Tetrahydro-as-indacenyl catalyst composition, catalyst system, and processes for use thereof

ABSTRACT

This invention relates to a compound represented by the formula: TyLAMXn-2 wherein: A is a substituted or unsubstituted tetrahydro-as-indacenyl group bonded to M; L is substituted or unsubstituted monocyclic or polycyclic arenyl ligand or monocyclic or polycyclic heteroarenyl ligand bonded to M; M is a group 3, 4, 5, or 6 transition metal (preferably group 4); T is a bridging group bonded to L and A; y is 0 or 1, indicating the absence or presence of T; X is a leaving group, typically a univalent anionic ligand, or two Xs are joined and bound to the metal atom to form a metallocycle ring, or two Xs are joined to form a chelating ligand, a diene ligand, or an alkylidene; n is the oxidation state of M and is 3, 4, 5, or 6.

PRIORITY CLAIM

This application is the 371 National Stage application of PCT/US2017/025400, filed Mar. 31, 2017, which is a continuation of U.S. Ser. No. 15/145,320, now U.S. Pat. No. 9,803,037, filed May 3, 2016 and are incorporated by reference in their entirety.

FIELD OF THE INVENTION

This invention relates to novel transition metal compounds, catalyst systems comprising such and polymerization process using such. This invention also relates to novel substituted tetrahydro-as-indacene and a method to produce substituted or unsubstituted tetrahydro-as-indacene.

BACKGROUND OF THE INVENTION

Olefin polymerization catalysts are of great use in industry. Hence, there is interest in finding new catalyst systems that increase the commercial usefulness of the catalyst and allow the production of polymers having improved properties.

Catalysts for olefin polymerization are often based on transition metal compounds as catalyst precursors, which are activated either with an alumoxane or with an activator containing a non-coordinating anion. A typical catalyst system includes a metallocene catalyst and an activator, and an optional support. Many metallocene catalyst systems can be used in homogeneous polymerizations (such as solution or supercritical) and supported catalyst systems are used in many polymerization processes, often in slurry or gas phase polymerization processes.

WO 2004/013149 A1 discloses group 4 metal constrained geometry complexes of tricyclic 4-aryl substituted indenyl ligands, esp. 1,5,6,7-tetrahydro-4-aryl-s-indacen-1-yl ligands, where the tetrahydro-s-indacene is substituted in the 4 position with a C₆₋₁₂ aryl group, and is preferably not substituted in the 5, 6, or 7 position, and if substituted in the 5, 6, or 7 position, is substituted by at most only one substituent at each position.

U.S. Pat. No. 6,420,507 discloses substituted tetrahydro-s-indacenyl transition metal complexes (such as Examples H to N), where the tetrahydro-s-indacene is not substituted the 5, 6, or 7 position and is substituted in the 2 and/or 3 position.

EP 1 120 424 (and family member U.S. Pat. No. 6,613,713) disclose tert-butylamino-2-(5,6,7-tetrahydro-s-indacenyldimethylsilyl) titanium dichloride indenyl ligands as polymerization catalyst where the tetrahydro-s-indacene is not substituted the 5, 6, or 7 position.

WO 2001/042315 discloses dimethylsilylene(t-butylamido)(2-methyl-tetrahydro-s-indacenyl)Ti(CH₂SiMe₃)₂ (see examples 27 and 28, and compounds IB5 and IB5′ in claim 21) as polymerization catalysts where the tetrahydro-s-indacene is not substituted the 5, 6, or 7 position.

WO 98/27103 discloses dimethylsilylene(t-butylamido)(2-methyl-tetrahydro-s-indacenyl)TiCl₂ (see example 1) and others as polymerization catalysts where the tetrahydro-s-indacene is not substituted the 5, 6, or 7 position.

Tuor, et al. (Journal of the American Chemical Society 136 (36), 12794-12798 (2014)) disclose Mono- and trinuclear sumanenyl zirconocene complexes Cp(sumanenyl)ZrCl₂, Cp*(sumanenyl)ZrCl₂, and (C₂₁H₉)[(Cp*)ZrCl₂]₃.

Kociolek, et al. (Tetrahedron Letters (1999), 40(22), 4141-4144) discloses flash vapor pyrolysis tetrahydro-[as]-indacene ligand.

Other references of interest include: U.S. Pat. Nos. 5,382,630; 5,382,631; 8,575,284; 6,069,213; Kim, J. D. et al., J. Polym. Sci. Part A: Polym Chem., 38, 1427 (2000); Iedema, P. D. et al., Ind. Eng. Chem. Res., 43, 36 (2004); U.S. Pat. Nos. 6,656,866; 8,815,357; US 2014/0031504; U.S. Pat. Nos. 5,135,526; 7,385,015; WO 2007/080365; WO2012/006272; WO2014/0242314; WO 00/12565; WO 02/060957; WO 2004/046214; U.S. Pat. Nos. 6,846,770; 6,664,348; WO 05/075525; US 2002/007023; WO 2003/025027; US 2005/0288461; US 2014/0031504; U.S. Pat. Nos. 8,088,867; 5,516,848; 4,701,432; 5,077,255; 7,141,632; 6,207,606; 8,598,061; Polymer Engineering and Science-2007, DOI 10.1002/pen, pages 131-139, published online in Wiley InterScience (www.interscience.wiley.com) 2007 Society of Plastics Engineers; US 2012/0130032; U.S. Pat. Nos. 7,192,902; 8,110,518; 9,193,856; 7,355,058; U.S. Ser. No. 62/149,799, filed Apr. 20, 2015 (and all cases claiming priority to or the benefit of U.S. Ser. No. 62/149,799); U.S. Ser. No. 62/103,372, filed Jan. 14, 2015 (and all cases claiming priority to or the benefit of U.S. Ser. No. 62/103,372); and PCT/US2015/067582, filed Dec. 28, 2015.

There is still a need in the art for new and improved catalyst systems for the polymerization of olefins, in order to achieve increased activity or specific polymer properties, such as high melting point, high molecular weights, to increase conversion or comonomer incorporation, or to alter comonomer distribution without deteriorating the resulting polymer's properties.

It is therefore also an object of the present invention to provide novel supported catalysts systems and processes for the polymerization of olefins using such catalyst systems.

The metallocene compounds and catalyst systems described herein address these needs by producing highly active catalysts containing a higher comonomer incorporation and molecular weight, that when formed into a molded part has improved properties (such as improved strength).

SUMMARY OF THE INVENTION

This invention relates to transition metal compounds represented by the formula: T_(y)LAMX_(n-2) wherein: A is a substituted or unsubstituted tetrahydro-as-indacenyl group bonded to M; L is substituted or unsubstituted monocyclic or polycyclic arenyl ligand or monocyclic or polycyclic heteroarenyl ligand bonded to M; M is a group 3, 4, 5, or 6 transition metal (preferably group 4); T is a bridging group bonded to L and A; y is 0 or 1, indicating the absence or presence of T; X is a leaving group, typically a univalent anionic ligand, or two Xs are joined and bound to the metal atom to form a metallocycle ring, or two Xs are joined to form a chelating ligand, a diene ligand, or an alkylidene; n is the oxidation state of M and is 3, 4, 5, or 6.

This invention also relates to a catalyst system comprising the bridged transition metal compound described herein and an activator.

This invention also relates to a process to produce olefin polymer comprising: i) contacting olefin and optional C₂ to C₂₀ comonomer with a catalyst system comprising activator and bridged transition metal compound described herein, and ii) obtaining an olefin polymer.

This invention also relates to transition metal catalyst compositions comprising the reaction product of: (1) one or more bridged transition metal compounds described above; (2) one or more activators.

This invention further relates to polymer compositions produced by the methods described herein.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph of isotactic polypropylene (iPP) Mn vs. Tm for catalyst A (black) and comparatives C-1 (dark grey), C-2 (light grey) and C-7 (white) at 70 (squares) and 100° C. (circles) polymerization temperature. A higher melting temperature correlates with increased isotacticity for the polymer produced from catalyst A vs. the comparatives.

FIG. 2 is a graph of catalyst activity vs. iPP Tm for catalyst A (black) and comparatives C-1 (dark grey), C-2 (light grey) and C-7 (white) at 70 (squares) and 100° C. (circles) polymerization temperature. Catalyst A provides significantly higher activity and iPP Tm for a given polymerization temperature.

FIG. 3 is a graph of iPP Mn vs. Tm for catalyst for catalyst C (black) and comparatives C-3 (grey) and C-4 (white) at 70 (squares) and 100° C. (circles) polymerization temperature. Catalyst C provides both higher polymer Tm and Mn at a given polymerization temperature vs. the comparatives.

FIG. 4 is a graph of iPP Mn vs. Tm for catalyst E (black) and comparatives C-5 (grey) and C-6 (white) at 70 (squares) and 100° C. (circles) polymerization temperature. Catalyst E provides both higher polymer Tm and Mn at a given polymerization temperature vs. the comparatives.

FIG. 5 is a graph of catalyst activity vs. iPP Tm for catalyst for catalyst E (black) and comparatives C-5 (grey) and C-6 (white) at 70 (squares) and 100° C. (circles) polymerization temperature. Catalyst E provides significantly higher activity and iPP Tm for a given polymerization temperature.

FIG. 6 is a graph of iPP Mn vs. Tm for catalyst L (black) and comparatives C-9 (grey) and C-10 (white) at 70 (squares) and 100° C. (circles) polymerization temperature. Catalyst L provides both higher polymer Tm and Mn at a given polymerization temperature vs. the comparatives.

FIG. 7 is a graph of catalyst activity vs. iPP Tm for catalyst L (black) and comparatives C-9 (grey) and C-10 (white) at 70 (squares) and 100° C. (circles) polymerization temperature. Catalyst L provides significantly higher activity and iPP Tm for a given polymerization temperature.

DETAILED DESCRIPTION OF THE INVENTION

For the purposes of this invention and the claims thereto, the new numbering scheme for the Periodic Table Groups is used as described in CHEMICAL AND ENGINEERING NEWS, 63(5), pg. 27 (1985), e.g., a “Group 4 metal” is an element from Group 4 of the Periodic Table, e.g., Hf, Ti, or Zr.

An “olefin,” alternatively referred to as “alkene,” is a linear, branched, or cyclic compound of carbon and hydrogen having at least one carbon-carbon double bond. For purposes of this specification and the claims appended thereto, when a polymer or copolymer is referred to as comprising an olefin, the olefin present in such polymer or copolymer is the polymerized form of the olefin. For example, when a copolymer is said to have an “ethylene” content of 35 wt % to 55 wt %, it is understood that the mer unit in the copolymer is derived from ethylene in the polymerization reaction and said derived units are present at 35 wt % to 55 wt %, based upon the weight of the copolymer. A “polymer” has two or more of the same or different mer units. A “homopolymer” is a polymer having mer units that are the same. A “copolymer” is a polymer having two or more mer units that are different from each other. A “terpolymer” is a polymer having three mer units that are different from each other. “Different” as used to refer to mer units indicates that the mer units differ from each other by at least one atom or are different isomerically. Accordingly, the definition of copolymer, as used herein, includes terpolymers and the like. An “ethylene polymer” or “ethylene copolymer” is a polymer or copolymer comprising at least 50 mole % ethylene derived units, a “propylene polymer” or “propylene copolymer” is a polymer or copolymer comprising at least 50 mole % propylene derived units, and so on.

For the purposes of this invention, ethylene shall be considered an α-olefin.

The terms “hydrocarbyl radical,” “hydrocarbyl,” and “hydrocarbyl group” are used interchangeably throughout this document. Likewise the terms “group,” “radical,” and “substituent” are also used interchangeably in this document. For purposes of this disclosure, “hydrocarbyl radical” is defined to be a radical, which contains hydrogen atoms and up to 50 carbon atoms and which may be linear, branched, or cyclic, and when cyclic, aromatic or non-aromatic.

Substituted hydrocarbyl radicals are radicals in which at least one hydrogen atom has been substituted with at least one functional group such as NR^(x) ₂, OR^(x), SeR^(x), TeR^(x), PR^(x) ₂, AsR^(x) ₂, SbR^(x) ₂, SR^(x), BR^(x), and the like, or where at least one non-hydrocarbon atom or group has been inserted within the hydrocarbyl radical, such as —O—, —S—, —Se—, —Te—, —N(R)—, ═N—, —P(R^(x))—, ═P—, —As(R^(x))—, ═As—, —Sb(R^(x))—, ═Sb—, —B(R^(x))—, ═B—, and the like, where R^(x) is independently a hydrocarbyl or halocarbyl radical, and two or more R^(x) may join together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure. Examples of a substituted hydrocarbyls would include —CH₂CH₂—O—CH₃ and —CH₂—NMe₂ where the radical is bonded via the carbon atom, but would not include groups where the radical is bonded through the heteroatom such as —OCH₂CH₃ or —NMe₂.

Silylcarbyl radicals are radicals in which one or more hydrocarbyl hydrogen atoms have been substituted with at least one SiR*₃ containing group or where at least one —Si(R*)₂— has been inserted within the hydrocarbyl radical where R* is independently a hydrocarbyl or halocarbyl radical, and two or more R* may join together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure.

Substituted silylcarbyl radicals are radicals in which at least one hydrogen atom has been substituted with at least one functional group such as NR*₂, OR*, SeR*, TeR*, PR*₂, AsR*₂, SbR*₂, SR*, BR*₂, GeR*₃, SnR*₃, PbR*₃ and the like or where at least one non-hydrocarbon atom or group has been inserted within the silylcarbyl radical, such as —O—, —S—, —Se—, —Te—, —N(R*)—, ═N—, —P(R*)—, ═P—, —As(R*)—, ═As—, —Sb(R*)—, ═Sb—, —B(R*)—, ═B—, —Ge(R*)₂—, —Sn(R*)₂—, —Pb(R*)₂—, and the like, where R* is independently a hydrocarbyl or halocarbyl radical, and two or more R* may join together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure. Substituted silylcarbyl radicals are only bonded via a carbon or silicon atom.

Germylcarbyl radicals are radicals in which one or more hydrocarbyl hydrogen atoms have been substituted with at least one GeR*₃ containing group or where at least one —Ge(R*)₂— has been inserted within the hydrocarbyl radical where R* independently a hydrocarbyl or halocarbyl radical, and two or more R* may join together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure. Substituted germylcarbyl radicals are only bonded via a carbon or germanium atom.

Substituted germylcarbyl radicals are radicals in which at least one hydrogen atom has been substituted with at least one functional group such as NR*₂, OR*, SeR*, TeR*, PR*₂, AsR*₂, SbR*₂, SR*, BR*₂, SiR*₃, SnR*₃, PbR*₃ and the like or where at least one non-hydrocarbon atom or group has been inserted within the germylcarbyl radical, such as —O—, —S—, —Se—, —Te—, —N(R*)—, ═N—, —P(R*)—, ═P—, —As(R*)—, ═As—, —Sb(R*)—, ═Sb—, —B(R*)—, ═B—, —Si(R*)₂—, —Sn(R*)₂—, —Pb(R*)₂—, and the like, where R* is independently a hydrocarbyl or halocarbyl radical, and two or more R* may join together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure.

Halocarbyl radicals are radicals in which one or more hydrocarbyl hydrogen atoms have been substituted with at least one halogen (e.g., F, Cl, Br, I) or halogen-containing group (e.g., CF₃).

Substituted halocarbyl radicals are radicals in which at least one halocarbyl hydrogen or halogen atom has been substituted with at least one functional group such as NR*₂, OR*, SeR*, TeR*, PR*₂, AsR*₂, SbR*₂, SR*, BR*₂, and the like, or where at least one non-carbon atom or group has been inserted within the halocarbyl radical such as —O—, —S—, —Se—, —Te—, —N(R*)—, ═N—, —P(R*)—, ═P—, —As(R*)—, ═As—, —Sb(R*)—, ═Sb—, —B(R*)—, ═B—, and the like, where R* is independently a hydrocarbyl or halocarbyl radical provided that at least one halogen atom remains on the original halocarbyl radical. Additionally, two or more R* may join together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure. Substituted halocarbyl radicals are only bonded via a carbon atom.

A heteroatom is an atom other than carbon or hydrogen.

The term “aryl” or “aryl group” means a monocyclic or polycyclic aromatic ring and the substituted variants thereof, including but not limited to, phenyl, naphthyl, 2-methyl-phenyl, xylyl, 4-bromo-xylyl. Likewise “heteroaryl” means an aryl group where a ring carbon atom (or two or three ring carbon atoms) has been replaced with a heteroatom, such as N, O, or S. The term “substituted aryl” means: 1) an aryl group where a hydrogen has been replaced by a substituted or unsubstituted hydrocarbyl group, a substituted or unsubstituted halocarbyl group, a substituted or unsubstituted silylcarbyl group, or a substituted or unsubstituted germylcarbyl group. The term “substituted heteroaryl” means: 1) a heteroaryl group where a hydrogen has been replaced by a substituted or unsubstituted hydrocarbyl group, a substituted or unsubstituted halocarbyl group, a substituted or unsubstituted silylcarbyl group, or a substituted or unsubstituted germylcarbyl group.

The following numbering schemes are used herein for cyclopentadienyl, indenyl, fluorenyl, and cyclopentanaphthyl (also termed benzindenyl). It should be noted that indenyl can be considered a cyclopentadienyl fused with a benzene ring. Analogously, fluorenyl can be considered a cyclopentadienyl with two phenyl rings fused onto the cyclopentadienyl ring. Each structure below is drawn and named as an anion.

The following numbering schemes are used herein for indenyl, tetrahydro-s-indacenyl and tetrahydro-as-indacenyl ligands.

The term “arenyl” ligand is used herein to mean a substituted or unsubstituted unsaturated cyclic hydrocarbyl ligand that can consist of one ring, or two or more fused or catenated rings. Cyclopentadienyl ligands, indenyl ligands, and fluorenyl ligands are all examples of arenyl ligands. The term “heteroarenyl” ligand is used herein to mean a heteroatom substituted arenyl ligand wherein one or more heteroatom(s) is part of the ring structure. Common heteroatoms include B, N, O, Si, P, and S.

The term “monocyclic arenyl ligand” is used herein to mean a substituted or unsubstituted monoanionic C₅ to C₁₀₀ hydrocarbyl ligand that contains an aromatic five-membered single hydrocarbyl ring (also referred to as a cyclopentadienyl ring).

The term “polycyclic arenyl ligand” is used herein to mean a substituted or unsubstituted monoanionic C₈ to C₁₀₃ hydrocarbyl ligand that contains an aromatic five-membered hydrocarbyl ring (also referred to as a cyclopentadienyl ring) that is fused to one or two partially unsaturated, or aromatic hydrocarbyl ring structures which may be fused to additional saturated, partially unsaturated, or aromatic hydrocarbyl rings.

Non-limiting examples of polycyclic arenyl ligands, are those listed in U.S. Pat. No. 7,446,216 at column 12, line 61 to column 14, line 31.

Partially hydrogenated polycyclic arenyl ligands retain the numbering scheme of the parent polycyclic arenyl ligand, namely the numbering schemes defined for indenyl, fluorenyl, cyclopenta[b]naphthyl, and cyclopenta[a]naphthyl ligands.

A “bondable ring position” is a ring position that is capable of bearing a substituent or bridging substituent. For example, cyclopenta[b]thienyl has five bondable ring positions (at the carbon atoms) and one non-bondable ring position (the sulfur atom); cyclopenta[b]pyrrolyl has six bondable ring positions (at the carbon atoms and at the nitrogen atom).

In using the terms “substituted or unsubstituted cyclopentadienyl ligand,” “substituted or unsubstituted indenyl ligand,” “substituted or unsubstituted fluorenyl ligand,” “substituted or unsubstituted cyclopentanaphthyl ligand,” “substituted or unsubstituted tetrahydro-as-indaceneyl ligand”, “substituted or unsubstituted monocyclic arenyl ligand,” or “substituted or unsubstituted polycyclic arenyl ligand,” the substitution to the aforementioned ligand is on a bondable ring position, and each occurrence is selected from hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, germylcarbyl, a halogen radical, or a polar group.

A “tetrahydro-as-indecenyl” ligand is defined to mean a substituted or unsubstituted unsaturated cyclic hydrocarbyl ligand that consists of at least one cyclopentadienyl ring fused to at least one six membered aromatic ring which is fused to at least one saturated five membered ring, typically represented by the formula:

where 1, 2, 3, 4, 5, 6, 7, and 8 indicate bondable ring positions.

Both isomers of substituted and unsubstituted tetrahydro-as-indecene compounds are typically named with the numbering scheme illustrated below:

As used herein, Mn is number average molecular weight, Mw is weight average molecular weight, and Mz is z average molecular weight, wt % is weight percent, and mol % is mole percent. Molecular weight distribution (MWD), also referred to as polydispersity, is defined to be Mw divided by Mn. Unless otherwise noted, all molecular weight units (e.g., Mw, Mn, Mz) are g/mol. The following abbreviations may be used herein: Me is methyl, Et is ethyl, Pr is propyl, cPr is cyclopropyl, nPr is n-propyl, iPr is isopropyl, Bu is butyl, nBu is normal butyl, iBu is isobutyl, sBu is sec-butyl, tBu is tert-butyl, Oct is octyl, Ph is phenyl, Bn is benzyl, Cp is cyclopentadienyl, Ind is indenyl, Flu is fluorenyl, and MAO is methylalumoxane.

For purposes of this invention and the claims thereto, a “catalyst system” is the combination of at least one catalyst compound, at least one activator, an optional co-activator, and an optional support material. For the purposes of this invention and the claims thereto, when catalyst systems are described as comprising neutral stable forms of the components, it is well understood by one of ordinary skill in the art, that the ionic form of the component is the form that reacts with the monomers to produce polymers.

In the description herein, the metallocene catalyst may be described as a catalyst precursor, a pre-catalyst compound, metallocene catalyst compound or a transition metal compound, and these terms are used interchangeably.

A metallocene catalyst is defined as an organometallic transition metal compound with at least one π-bound arenyl moiety such as cyclopentadienyl (or substituted arenyl moiety such as 2-methylindenyl) bound to a transition metal.

For purposes of this invention and claims thereto in relation to metallocene catalyst compounds, the term “substituted” means that one or more hydrogen atoms have been replaced with a hydrocarbyl, heteroatom (such as a halide), or a heteroatom containing group, (such as silylcarbyl, germylcarbyl, halocarbyl, etc.). For example, methyl cyclopentadiene (Cp) is a Cp group substituted with a methyl group.

For purposes of this invention and claims thereto, “alkoxides” include those where the alkyl group is a C₁ to C₁₀ hydrocarbyl. The alkyl group may be straight chain, branched, or cyclic. The alkyl group may be saturated or unsaturated. In some embodiments, the alkyl group may comprise at least one aromatic group.

Embodiments

This invention relates to tetrahydro-as-indacenyl metallocene catalyst compounds, catalyst systems comprising such compounds and an optional support and polymerization processes using such.

This invention relates to transition metal compounds represented by the formula: T_(y)LAMX_(n-2) A is a substituted or unsubstituted tetrahydro-as-indacenyl group bonded to M; L is substituted or unsubstituted monocyclic or polycyclic arenyl ligand or monocyclic or polycyclic heteroarenyl ligand bonded to M; M is a group 3, 4, 5, or 6 transition metal, preferably group 4 transition metal, for example titanium, zirconium, or hafnium (preferably zirconium or hafnium); T is a bridging group (such as dialkylsilylene or dialkylcarbylene); T is preferably (CR⁸R⁹)_(x), SiR⁸R⁹ or GeR⁸R⁹ where x is 1 or 2, R⁸ and R⁹ are independently selected from substituted or unsubstituted hydrocarbyl, halocarbyl, silylcarbyl and germylcarbyl and R⁸ and R⁹ may optionally be bonded together to form a ring structure; y is 0 or 1, indicating the absence or presence of T; X is a leaving group, typically a univalent anionic ligand such as a halide, a hydride, an alkyl group, an alkenyl group or an arylalkyl group, or two Xs are joined and bound to the metal atom to form a metallocycle ring, or two Xs are joined to form a chelating ligand, a diene ligand, or an alkylidene; and n is the oxidation state of M and is 3, 4, 5, or 6, preferably 4.

This invention relates to a catalyst system comprising an activator, and at least one metallocene catalyst compound, where the metallocene is a tetrahydro-as-indacenyl transition metal compound, preferably represented by the formula: T_(y)LAMX_(n-2) A is a substituted or unsubstituted tetrahydro-as-indacenyl group bonded to M; L is substituted or unsubstituted monocyclic or polycyclic arenyl ligand or monocyclic or polycyclic heteroarenyl ligand bonded to M; M is a group 3, 4, 5, or 6 transition metal, preferably group 4 transition metal, for example titanium, zirconium, or hafnium (preferably zirconium or hafnium); T is a bridging group (such as dialkylsilylene or dialkylcarbylene) bonded to L and A; T is preferably (CR⁸R⁹)_(x), SiR⁸R⁹ or GeR⁸R⁹ where x is 1 or 2, R⁸ and R⁹ are independently selected from substituted or unsubstituted hydrocarbyl, halocarbyl, silylcarbyl and germylcarbyl and R⁸ and R⁹ may optionally be bonded together to form a ring structure; y is 0 or 1, indicating the absence or presence of T; X is a leaving group, typically a univalent anionic ligand such as a halide, a hydride, an alkyl group, an alkenyl group or an arylalkyl group, or two Xs are joined and bound to the metal atom to form a metallocycle ring, or two Xs are joined to form a chelating ligand, a diene ligand, or an alkylidene; and n is the oxidation state of M and is 3, 4, 5, or 6, preferably 4. Catalyst Compounds and Ligands

This invention relates to transition metal compounds comprising a tetrahydro-as-indacenyl ligand wherein the ligand is derived from tetrahydro-as-indacene isomers represented by the formulas (4a and 4b):

wherein R¹, R², R⁴, R⁵, and each R^(a), R^(b), and R^(c) are as defined below for Formulas 1 and 2, and R³ is hydrogen or hydrocarbyl, preferable hydrogen. Preferably, at least one R^(a), R^(b) and R^(c) is not hydrogen. This invention also relates to the tetrahydro-as-indacene compounds of Formulas 4a and 4b wherein R¹, R², R⁴, R⁵, and each R^(a), R^(b) and R^(c) are as defined below for Formulas 1 and 2, and R³ is hydrogen or hydrocarbyl, preferably hydrogen.

This invention further relates to tetrahydro-as-indacenyl transition metal compounds represented by the formula 2 or 3:

wherein M is a group 3, 4, 5, or 6 transition metal, preferably group 4 transition metal, for example titanium, zirconium, or hafnium (preferably zirconium or hafnium); B is the oxidation state of M and is 3, 4, 5, or 6, preferably 4; C is B-2; T is a bridging group; y is 1 or 0 indicating the presence of absence of T; X is a leaving group, typically a univalent anionic ligand such as a halide, a hydride, an alkyl group, an alkenyl group or an arylalkyl group, or two Xs are joined and bound to the metal atom to form a metallocycle ring, or two Xs are joined to form a chelating ligand, a diene ligand, or an alkylidene; L is a substituted or unsubstituted monocyclic or polycyclic arenyl ligand or monocyclic or polycyclic heteroarenyl ligand bonded (typically pi-bonded) to M; each R¹, R², R⁴, and R⁵ is independently hydrogen, or a C₁-C₅₀ substituted or unsubstituted hydrocarbyl, halocarbyl or silylcarbyl; and each R^(a), R^(b), and R^(c) is independently a C₁-C₅₀ substituted or unsubstituted hydrocarbyl (preferably a C₁-C₁₀ alkyl), or hydrogen.

In any embodiment of the invention, each R^(a), R^(b), R^(c), R¹, R², R⁴ and R⁵ is independently hydrogen or a C₁-C₅₀ substituted or unsubstituted hydrocarbyl.

In any embodiment of the invention, each R^(a), R^(b), R^(c), R¹, R², R⁴, and R⁵ is independently hydrogen or a C₁-C₁₀ alkyl.

In any embodiment of the invention, each R^(b) and R² is independently a C₁-C₁₀ alkyl and each R^(a), R^(c), R¹, R⁴, and R⁵ is hydrogen.

In any embodiment of the invention, each R^(b) is independently a C₁-C₁₀ alkyl and each R^(a), R^(c), R¹, R², R⁴, and R⁵ is hydrogen.

In any embodiment of the invention each R² is independently a C₁-C₁₀ alkyl and each R^(a), R^(b), R^(c), R¹, R⁴, and R⁵ is hydrogen.

In any embodiment of the invention, each R^(b) and R² is independently methyl, ethyl, or an isomer of propyl, butyl, pentyl or hexyl, and each R^(a), R^(c), R¹, R⁴, and R⁵ is hydrogen.

In any embodiment of the invention, each R² is methyl, ethyl, or an isomer of propyl, butyl, pentyl or hexyl, and each R^(a), R^(b), R^(c), R¹, R⁴, and R⁵ is hydrogen.

In any embodiment of the invention, each R^(b) and R² is independently methyl or ethyl and each R^(a), R^(c), R¹, R⁴, and R⁵ is hydrogen.

In any embodiment of the invention, each R² is methyl or ethyl and R^(a), R^(b), R^(c), R¹, R⁴, and R⁵ are hydrogen.

In any embodiment of the invention, each R² is independently hydrogen, methyl, ethyl, propyl, butyl, pentyl or hexyl.

In any embodiment of the invention, each R² is independently hydrogen, methyl or ethyl.

In any embodiment of the invention, each R² is methyl or ethyl.

In any embodiment of the invention, each R^(b) is independently hydrogen, methyl, ethyl, propyl, butyl, pentyl or hexyl.

In any embodiment of the invention, each R^(b) is independently hydrogen, methyl or ethyl.

In any embodiment of the invention, each R^(b) is methyl or ethyl.

In any embodiment of the invention, each R^(a) and R^(c) is independently hydrogen, methyl or ethyl.

In any embodiment of the invention, each R^(a) and R^(c) is independently hydrogen.

In any embodiment of the invention, T is selected from (CR⁸R⁹)_(x), (SiR¹⁰R¹¹)_(x), CR⁸R⁹SiR¹⁰R¹¹, GeR¹⁰R¹¹, BR¹², NR¹², PR¹², O, or S where x is 1 or 2, R⁸ and R⁹ are independently selected from hydrogen, substituted or unsubstituted hydrocarbyl, halocarbyl, silylcarbyl, R¹⁰, R¹¹, and R¹² are independently selected from substituted or unsubstituted hydrocarbyl, halocarbyl, silylcarbyl and any two or more adjacent R⁸, R⁹, R¹⁰, or R¹¹ may optionally be bonded together to form a ring structure.

In any embodiment of the invention, T is selected from (CR⁸R⁹)_(x), (SiR¹⁰11⁹)_(x), or GeR¹⁰R¹¹ where x is 1 or 2, R⁸, R⁹, R¹⁰, and R¹¹ are as defined above.

In any embodiment of the invention, T is selected from diphenylmethylene, dimethylmethylene, 1,2-ethylene, cyclotrimethylenesilylene, cyclotetramethylenesilylene, cyclopentamethylenesilylene, dimethylsilylene, diethylsilylene, methylethylsilylene, methylphenylsilylene, diphenylsilylene, dipropylsilylene and 1,2-tetramethyldisilylene.

In any embodiment of the invention, T is selected from cyclotetramethylenesilylene, dimethylsilylene, and 1,2-tetramethyldisilylene.

In any embodiment of the invention, each X is hydrocarbyl, halocarbyl, or substituted hydrocarbyl or halocarbyl.

In any embodiment of the invention, X is methyl, benzyl, or halo where halo includes fluoride, chloride, bromide and iodide.

In any embodiment of any formula described herein, y is 1 and T is a bridging group containing at least one Group 13, 14, 15, or 16 element, in particular boron or a Group 14, 15 or 16 element. Examples of suitable bridging groups include P(═S)R*, P(═Se)R*, P(═O)R*, R*₂C, R*₂Si, R*₂Ge, R*₂CCR*₂, R*₂CCR*₂CR*₂, R*₂CCR*₂CR*₂CR*₂, R*C═CR*, R*C═CR*CR*₂, —R*₂CCR*═CR*CR*₂, —R*C═CR*CR*═CR*, —R*C═CR*CR*₂CR*₂, R*₂CSiR*₂, R*₂SiSiR*₂, R*₂SiOSiR*₂, R*₂CSiR*₂CR*₂, R*₂SiCR*₂SiR*₂, R*C═CR*SiR*₂, R*₂CGeR*₂, R*₂GeGeR*₂, —R*₂CGeR*₂CR*₂, R*₂GeCR*₂GeR*₂, R*₂SiGeR*₂, R*C═CR*GeR*₂, R*B, R*₂C—BR*, R*₂C—BR*—CR*₂, R*₂C—O—CR*₂, R*₂CR*₂C—O—CR*₂CR*₂, R*₂C—O—CR*₂CR*₂, R*₂C—O—CR*═CR*, R*₂C—S—CR*₂, R*₂CR*₂C—S—CR*₂CR*₂, R*₂C—S—CR*₂CR*₂, R*₂C—S—CR*═CR*, R*₂C—Se—CR*₂, R*₂CR*₂C—Se—CR*₂CR*₂, R*₂C—Se—CR*₂CR*₂, R*₂C—Se—CR*═CR*, R*₂C—N═CR*, R*₂C—NR*—CR*₂, R*₂C—NR*—CR*₂CR*₂, —R*₂C—NR*—CR*═CR*, —R*₂CR*₂C—NR*—CR*₂CR*₂, —R*₂C—P═CR*, R*₂C—PR*—CR*₂, O, S, Se, Te, NR*, PR*, AsR*, SbR*, O—O, S—S, R*N—NR*, R*P—PR*, O—S, O—NR*, O—PR*, S—NR*, S—PR*, and R*N—PR* where R* is hydrogen or a C₁-C₂₀ containing hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl or germylcarbyl substituent and optionally two or more adjacent R* may join to form a substituted or unsubstituted, saturated, partially unsaturated or aromatic, cyclic or polycyclic substituent. Preferred examples for the bridging group T include CH₂, CH₂CH₂, SiMe₂, SiPh₂, SiMePh, Si(CH₂)₃, Si(CH₂)₄, O, S, NPh, PPh, NMe, PMe, NEt, NPr, NBu, PEt, PPr, Me₂SiOSiMe₂, and PBu. In a preferred embodiment of the invention in any embodiment of any formula described herein, T is represented by the formula ER^(d) ₂ or (ER^(d) ₂)₂, where E is C, Si, or Ge, and each R^(d) is, independently, hydrogen, halogen, C₁ to C₂₀ hydrocarbyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl) or a C₁ to C₂₀ substituted hydrocarbyl, and two R^(d) can form a cyclic structure including aromatic, partially saturated, or saturated cyclic or fused ring system. Preferably, T is a bridging group comprising carbon or silica, such as dialkylsilyl, preferably T is selected from CH₂, —CH₂CH₂, —C(CH₃)₂, SiMe₂, cyclotrimethylenesilylene (Si(CH₂)₃), cyclopentamethylenesilylene (Si(CH₂)₅) and cyclotetramethylenesilylene (Si(CH₂)₄).

Illustrative, but not limiting, examples of preferred metallocenes for use in this invention's mixed catalyst composition include:

-   dimethylsilylene(2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(indenyl)M(R)₂,     cyclotetramethylenesilylene(2,7,7-trimethyl-1,6,7,8-tetrahydro-as-indacen-3-yl)(indenyl)M(R)₂,     dimethylsilylene(2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(cyclopentadienyl)M(R)₂,     cyclotetramethylenesilylene(2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(cyclopentadienyl)M(R)₂,     dimethylsilylene-bis(2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)M(R)₂,     cyclotetramethylenesilylene-bis(2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)M(R)₂,     cyclotrimethylenesilylene-bis(2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)M(R)₂,     ethylene-bis-(2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)M(R)₂,     dimethylmethylene-bis-(2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)M(R)₂,     tetramethyldisilanediyl-bis(2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)M(R)₂,     dimethylsilylene-bis(7,7-dimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)M(R)₂,     cyclotetramethylenesilylene-bis(7,7-dimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)M(R)₂,     cyclotrimethylenesilylene-bis(7,7-dimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)M(R)₂,     ethylene-bis-(7,7-dimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)M(R)₂,     dimethylmethylene-bis-(7,7-dimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)M(R)₂,     tetramethyldisilanediyl-bis(7,7-dimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)M(R)₂,     dimethylsilylene-bis(2-methyl-3,6,7,8-tetrahydro-as-indacen-3-yl)M(R)₂,     cyclotetramethylenesilylene-bis(2-methyl-3,6,7,8-tetrahydro-as-indacen-3-yl)M(R)₂,     cyclotrimethylenesilylene-bis(2-methyl-3,6,7,8-tetrahydro-as-indacen-3-yl)M(R)₂,     ethylene-bis-(2-methyl-3,6,7,8-tetrahydro-as-indacen-3-yl)M(R)₂,     dimethylmethylene-bis-(2-methyl-3,6,7,8-tetrahydro-as-indacen-3-yl)M(R)₂,     tetramethyldisilanediyl-bis(2-methyl-3,6,7,8-tetrahydro-as-indacen-3-yl)M(R)₂,     dimethylsilylene-bis(2,7,7-triethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)M(R)₂,     cyclotetramethylenesilylene-bis(2,7,7-triethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)M(R)₂,     cyclotrimethylenesilylene-bis(2,7,7-triethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)M(R)₂,     ethylene-bis-(2,7,7-triethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)M(R)₂,     dimethylmethylene-bis-(2,7,7-triethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)M(R)₂,     tetramethyldisilanediyl-bis(2,7,7-triethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)M(R)₂,     dimethylsilylene-bis(7,7-diethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)M(R)₂,     cyclotetramethylenesilylene-bis(7,7-diethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)M(R)₂,     cyclotrimethylenesilylene-bis(7,7-diethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)M(R)₂,     ethylene-bis-(7,7-diethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)M(R)₂,     dimethylmethylene-bis-(7,7-diethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)M(R)₂,     tetramethyldisilanediyl-bis(7,7-diethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)M(R)₂,     dimethylsilylene-bis(2-ethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)M(R)₂,     cyclotetramethylenesilylene-bis(2-ethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)M(R)₂,     cyclotrimethylenesilylene-bis(2-ethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)M(R)₂,     ethylene-bis-(2-ethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)M(R)₂,     dimethylmethylene-bis-(2-ethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)M(R)₂,     tetramethyldisilanediyl-bis(2-ethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)M(R)₂,     dimethylsilylene-bis(2-methyl-7,7-diethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)M(R)₂,     cyclotetramethylenesilylene-bis(2-methyl-7,7-diethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)M(R)₂,     cyclotrimethylenesilylene-bis(2-methyl-7,7-diethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)M(R)₂,     where M is selected from a group consisting of Ti, Zr, and Hf     (preferably Zr and Hf) and R is selected from halogen or C₁ to C₅     alkyl or benzyl, preferably R is a methyl group or a halogen group     (preferably C₁) and preferably M(R)₂ is ZrCl₂, ZrMe₂, HfCl₂ or     HfMe₂).

In alternate embodiments, two or more different transition metal compounds may be used herein. For purposes of this invention one transition metal compound is considered different from another if they differ by at least one atom. For example, “Me₂Si(2,7,7-Me₃-3,6,7,8-tetrahydro-as-indacen-3-yl)₂ ZrCl₂” is different from “Me₂Si(7,7-Me₂-3,6,7,8-tetrahydro-as-indacen-3-yl)₂ZrCl₂” which is different from “Me₂Si(2,7,7-Me₃-3,6,7,8-tetrahydro-as-indacen-3-yl)₂HfCl₂.”

In a preferred embodiment, one tetrahydro-as-indacenyl compound as described herein is used in the catalyst system.

Activators

The terms “cocatalyst” and “activator” are used herein interchangeably and are defined to be any compound which can activate any one of the catalyst compounds described above by converting the neutral catalyst compound to a catalytically active catalyst compound cation. Non-limiting activators, for example, include alumoxanes, aluminum alkyls, ionizing activators, which may be neutral or ionic, and conventional-type cocatalysts. Preferred activators typically include alumoxane compounds, modified alumoxane compounds, and ionizing anion precursor compounds that abstract a reactive, σ-bound, metal ligand making the metal complex cationic and providing a charge-balancing noncoordinating or weakly coordinating anion.

Alumoxane Activators

Alumoxane activators are utilized as activators in the catalyst systems described herein. Alumoxanes are generally oligomeric compounds containing —Al(R¹)—O— sub-units, where R¹ is an alkyl group. Examples of alumoxanes include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane and isobutylalumoxane. Alkylalumoxanes and modified alkylalumoxanes are suitable as catalyst activators, particularly when the abstractable ligand is an alkyl, halide, alkoxide or amide. Mixtures of different alumoxanes and modified alumoxanes may also be used. It may be preferable to use a visually clear methylalumoxane. A cloudy or gelled alumoxane can be filtered to produce a clear solution or clear alumoxane can be decanted from the cloudy solution. A useful alumoxane is a modified methyl alumoxane (MMAO) cocatalyst type 3A (commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylalumoxane type 3A, covered under patent number U.S. Pat. No. 5,041,584).

When the activator is an alumoxane (modified or unmodified), some embodiments select the maximum amount of activator typically at up to a 5000-fold molar excess Al/M over the catalyst compound (per metal catalytic site). The minimum activator-to-catalyst-compound is a 1:1 molar ratio. Alternate preferred ranges include from 1:1 to 500:1, alternately from 1:1 to 200:1, alternately from 1:1 to 100:1, or alternately from 1:1 to 50:1.

Non Coordinating Anion Activators

Non-coordinating anion activators may also be used herein. The term “non-coordinating anion” (NCA) means an anion which either does not coordinate to a cation or which is only weakly coordinated to a cation thereby remaining sufficiently labile to be displaced by a neutral Lewis base. “Compatible” non-coordinating anions are those which are not degraded to neutrality when the initially formed complex decomposes. Further, the anion will not transfer an anionic substituent or fragment to the cation so as to cause it to form a neutral transition metal compound and a neutral by-product from the anion. Non-coordinating anions useful in accordance with this invention are those that are compatible, stabilize the transition metal cation in the sense of balancing its ionic charge at +1, and yet retain sufficient lability to permit displacement during polymerization.

It is within the scope of this invention to use an ionizing or stoichiometric activator, neutral or ionic, such as tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, a tris perfluorophenyl boron metalloid precursor or a tris perfluoronaphthyl boron metalloid precursor, polyhalogenated heteroborane anions (WO 98/43983), boric acid (U.S. Pat. No. 5,942,459), in combination with the alumoxane or modified alumoxane activators. It is also within the scope of this invention to use neutral or ionic activators in combination with the alumoxane or modified alumoxane activators.

The catalyst systems of this invention can include at least one non-coordinating anion (NCA) activator. Specifically, the catalyst systems may include an NCAs which either do not coordinate to a cation or which only weakly coordinate to a cation thereby remaining sufficiently labile to be displaced during polymerization.

The terms “cocatalyst” and “activator” are used herein interchangeably and are defined to be any compound which can activate any one of the catalyst compounds described above by converting the neutral catalyst compound to a catalytically active catalyst compound cation.

In a preferred embodiment, boron containing NCA activators represented by the formula below can be used: Z_(d) ⁺(A^(d−)) where: Z is (L-H) or a reducible Lewis acid; L is a neutral Lewis base; H is hydrogen; (L-H) is a Bronsted acid; A^(d−) is a boron containing non-coordinating anion having the charge d−; d is 1, 2, or 3.

The cation component, Z_(d) ⁺ may include Bronsted acids such as protons or protonated Lewis bases or reducible Lewis acids capable of protonating or abstracting a moiety, such as an alkyl or aryl, from the bulky ligand metallocene containing transition metal catalyst precursor, resulting in a cationic transition metal species.

The activating cation Z_(d) ⁺ may also be a moiety such as silver, tropylium, carboniums, ferroceniums and mixtures, preferably carboniums and ferroceniums. Most preferably Z_(d) ⁺ is triphenyl carbonium. Preferred reducible Lewis acids can be any triaryl carbonium (where the aryl can be substituted or unsubstituted, such as those represented by the formula: (Ar₃C⁺), where Ar is aryl or aryl substituted with a heteroatom, a C₁ to C₄₀ hydrocarbyl, or a substituted C₁ to C₄₀ hydrocarbyl), preferably the reducible Lewis acids in formula (14) above as “Z” include those represented by the formula: (Ph₃C), where Ph is a substituted or unsubstituted phenyl, preferably substituted with C₁ to C₄₀ hydrocarbyls or substituted a C₁ to C₄₀ hydrocarbyls, preferably C₁ to C₂₀ alkyls or aromatics or substituted C₁ to C₂₀ alkyls or aromatics, preferably Z is a triphenylcarbonium.

When Z_(d) ⁺ is the activating cation (L-H)_(d) ⁺, it is preferably a Bronsted acid, capable of donating a proton to the transition metal catalytic precursor resulting in a transition metal cation, including ammoniums, oxoniums, phosphoniums, silyliums, and mixtures thereof, preferably ammoniums of methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo N,N-dimethylaniline, p-nitro-N,N-dimethylaniline, phosphoniums from triethylphosphine, triphenylphosphine, and diphenylphosphine, oxoniums from ethers such as dimethyl ether diethyl ether, tetrahydrofuran and dioxane, sulfoniums from thioethers, such as diethyl thioethers, tetrahydrothiophene, and mixtures thereof.

The anion component A^(d−) includes those having the formula [M^(k+)Q_(n)]^(d−) wherein k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6 (preferably 1, 2, 3, or 4); n-k=d; M is an element selected from Group 13 of the Periodic Table of the Elements, preferably boron or aluminum, and Q is independently a hydride, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, and halosubstituted-hydrocarbyl radicals, said Q having up to 20 carbon atoms with the proviso that in not more than 1 occurrence is Q a halide. Preferably, each Q is a fluorinated hydrocarbyl group having 1 to 20 carbon atoms, more preferably each Q is a fluorinated aryl group, and most preferably each Q is a pentafluoryl aryl group. Examples of suitable A^(d−) also include diboron compounds as disclosed in U.S. Pat. No. 5,447,895, which is fully incorporated herein by reference.

Illustrative, but, not limiting, examples of boron compounds which may be used as an activating cocatalyst are the compounds described as (and particularly those specifically listed as) activators in U.S. Pat. No. 8,658,556, which is incorporated by reference herein.

Most preferably, the ionic stoichiometric activator Z_(d) ⁺ (A^(d−)) is one or more of N,N-dimethylanilinium tetra(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, or triphenylcarbenium tetra(perfluorophenyl)borate.

Bulky activators are also useful herein as NCAs. “Bulky activator” as used herein refers to anionic activators represented by the formula:

where: each R₁ is, independently, a halide, preferably a fluoride; Ar is substituted or unsubstituted aryl group (preferably a substituted or unsubstituted phenyl), preferably substituted with C₁ to C₄₀ hydrocarbyls, preferably C₁ to C₂₀ alkyls or aromatics; each R₂ is, independently, a halide, a C₆ to C₂₀ substituted aromatic hydrocarbyl group or a siloxy group of the formula —O—Si—R_(a), where R_(a) is a C₁ to C₂₀ hydrocarbyl or hydrocarbylsilyl group (preferably R₂ is a fluoride or a perfluorinated phenyl group); each R₃ is a halide, C₆ to C₂₀ substituted aromatic hydrocarbyl group or a siloxy group of the formula —O—Si—R_(a), where R_(a) is a C₁ to C₂₀ hydrocarbyl or hydrocarbylsilyl group (preferably R₃ is a fluoride or a C₆ perfluorinated aromatic hydrocarbyl group); wherein R₂ and R₃ can form one or more saturated or unsaturated, substituted or unsubstituted rings (preferably R₂ and R₃ form a perfluorinated phenyl ring); and L is an neutral Lewis base; (L-H)⁺ is a Bronsted acid; d is 1, 2, or 3; wherein the anion has a molecular weight of greater than 1020 g/mol; wherein at least three of the substituents on the B atom each have a molecular volume of greater than 250 cubic Å, alternately greater than 300 cubic Å, or alternately greater than 500 cubic Å.

Preferably (Ar₃C)_(d) ⁺ is (Ph₃C)_(d) ⁺, where Ph is a substituted or unsubstituted phenyl, preferably substituted with C₁ to C₄₀ hydrocarbyls or substituted C₁ to C₄₀ hydrocarbyls, preferably C₁ to C₂₀ alkyls or aromatics or substituted C₁ to C₂₀ alkyls or aromatics.

“Molecular volume” is used herein as an approximation of spatial steric bulk of an activator molecule in solution. Comparison of substituents with differing molecular volumes allows the substituent with the smaller molecular volume to be considered “less bulky” in comparison to the substituent with the larger molecular volume. Conversely, a substituent with a larger molecular volume may be considered “more bulky” than a substituent with a smaller molecular volume.

Molecular volume may be calculated as reported in “A Simple ‘Back of the Envelope’ Method for Estimating the Densities and Molecular Volumes of Liquids and Solids,” Journal of Chemical Education, Vol. 71, No. 11, November 1994, pp. 962-964. Molecular volume (MV), in units of cubic Å, is calculated using the formula: MV=8.3V_(s), where V_(s) is the scaled volume. V_(s) is the sum of the relative volumes of the constituent atoms, and is calculated from the molecular formula of the substituent using the following table of relative volumes. For fused rings, the V_(s) is decreased by 7.5% per fused ring.

Element Relative Volume H 1 1^(st) short period, Li to F 2 2^(nd) short period, Na to Cl 4 1^(st) long period, K to Br 5 2^(nd) long period, Rb to I 7.5 3^(rd) long period, Cs to Bi 9

For a list of particularly useful Bulky activators please see U.S. Pat. No. 8,658,556, which is incorporated by reference herein.

In another embodiment, one or more of the NCA activators is chosen from the activators described in U.S. Pat. No. 6,211,105.

Preferred activators include N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluorophenyl)borate, [Ph₃C⁺][B(C₆F₅)₄ ⁻], [Me₃NH⁺][B(C₆F₅)₄ ⁻]; 1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium; and tetrakis(pentafluorophenyl)borate, 4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine.

In a preferred embodiment, the activator comprises a triaryl carbonium (such as triphenylcarbenium tetraphenylborate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate).

In another embodiment, the activator comprises one or more of trialkylammonium tetrakis(pentafluorophenyl)borate, N,N-dialkylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis(pentafluorophenyl)borate, trialkylammonium tetrakis-(2,3,4,6-tetrafluorophenyl) borate, N,N-dialkylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, trialkylammonium tetrakis(perfluoronaphthyl)borate, N,N-dialkylanilinium tetrakis(perfluoronaphthyl)borate, trialkylammonium tetrakis(perfluorobiphenyl)borate, N,N-dialkylanilinium tetrakis(perfluorobiphenyl)borate, trialkylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dialkylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dialkyl-(2,4,6-trimethylanilinium) tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate, (where alkyl is methyl, ethyl, propyl, n-butyl, sec-butyl, or t-butyl).

The typical NCA activator-to-catalyst ratio, e.g., all NCA activators-to-catalyst ratio is about a 1:1 molar ratio. Alternate preferred ranges include from 0.1:1 to 100:1, alternately from 0.5:1 to 200:1, alternately from 1:1 to 500:1 alternately from 1:1 to 1000:1. A particularly useful range is from 0.5:1 to 10:1, preferably 1:1 to 5:1.

Activators useful herein also include those described in U.S. Pat. No. 7,247,687 at column 169, line 50 to column 174, line 43, particularly column 172, line 24 to column 173, line 53.

It is also within the scope of this invention that the catalyst compounds can be combined with combinations of alumoxanes and NCA's (see for example, U.S. Pat. Nos. 5,153,157; 5,453,410; EP 0 573 120; WO 94/07928; and WO 95/14044, which discuss the use of an alumoxane in combination with an ionizing activator).

Optional Scavengers or Co-Activators

In addition to the activator compounds, scavengers, chain transfer agents or co-activators may be used. Aluminum alkyl or organoaluminum compounds which may be utilized as scavengers or co-activators include, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and diethyl zinc.

Useful chain transfer agents that may also be used herein are typically a compound represented by the formula AlR₃, ZnR₂ (where each R is, independently, a C₁-C₈ aliphatic radical, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl octyl or an isomer thereof) or a combination thereof, such as diethyl zinc, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or a combination thereof.

Supports

In some embodiments, the complexes described herein may be supported (with or without an activator) by any method effective to support other coordination catalyst systems, effective meaning that the catalyst so prepared can be used for oligomerizing or polymerizing olefin in a heterogeneous process. The catalyst precursor, activator, co-activator if needed, suitable solvent, and support may be added in any order or simultaneously. Typically, the complex and activator may be combined in solvent to form a solution. Then the support is added, and the mixture is stirred for 1 minute to 10 hours. The total solution volume may be greater than the pore volume of the support, but some embodiments limit the total solution volume below that needed to form a gel or slurry (about 90% to 400%, preferably about 100-200% of the pore volume). After stirring, the residual solvent is removed under vacuum, typically at ambient temperature and over 10-16 hours. But greater or lesser times and temperatures are possible.

The complex may also be supported absent the activator; in that case, the activator (and co-activator if needed) is added to a polymerization process's liquid phase. Additionally, two or more different complexes may be placed on the same support. Likewise, two or more activators or an activator and co-activator may be placed on the same support.

Suitable solid particle supports are typically comprised of polymeric or refractory oxide materials, each being preferably porous. Preferably, any support material that has an average particle size greater than 10 μm is suitable for use in this invention. Various embodiments select a porous support material, such as for example, talc, inorganic oxides, inorganic chlorides, for example, magnesium chloride and resinous support materials such as polystyrene polyolefin or polymeric compounds or any other organic support material and the like. Some embodiments select inorganic oxide materials as the support material including Group-2, -3, -4, -5, -13, or -14 metal or metalloid oxides. Some embodiments select the catalyst support materials to include silica, alumina, silica-alumina, and their mixtures. Other inorganic oxides may serve either alone or in combination with the silica, alumina, or silica-alumina. These are magnesia, titania, zirconia, and the like. Lewis acidic materials such as montmorillonite and similar clays may also serve as a support. In this case, the support can optionally double as the activator component; however, an additional activator may also be used.

The support material may be pretreated by any number of methods. For example, inorganic oxides may be calcined, chemically treated with dehydroxylating agents such as aluminum alkyls and the like, or both.

As stated above, polymeric carriers will also be suitable in accordance with the invention, see for example the descriptions in WO 95/15815 and U.S. Pat. No. 5,427,991. The methods disclosed may be used with the catalyst complexes, activators or catalyst systems of this invention to adsorb or absorb them on the polymeric supports, particularly if made up of porous particles, or may be chemically bound through functional groups bound to or in the polymer chains.

Useful supports typically have a surface area of from 10-700 m²/g, a pore volume of 0.1-4.0 cc/g and an average particle size of 10-500 μm. Some embodiments select a surface area of 50-500 m²/g, a pore volume of 0.5-3.5 cc/g, or an average particle size of 20-200 μm. Other embodiments select a surface area of 100-400 m²/g, a pore volume of 0.8-3.0 cc/g, and an average particle size of 30-100 μm. Useful supports typically have a pore size of 10-1000 Angstroms, alternatively 50-500 Angstroms, or 75-350 Angstroms.

The catalyst complexes described herein are generally deposited on the support at a loading level of 10-100 micromoles of complex per gram of solid support; alternately 20-80 micromoles of complex per gram of solid support; or 40-60 micromoles of complex per gram of support. But greater or lesser values may be used provided that the total amount of solid complex does not exceed the support's pore volume.

In an alternate embodiment, catalyst complexes and catalyst systems described herein may be present on a fluorided support, e.g., a support, desirably particulate and porous, which has been treated with at least one inorganic fluorine containing compound. For example, the fluorided support composition can be a silicon dioxide support wherein a portion of the silica hydroxyl groups has been replaced with fluorine or fluorine containing compounds. For example, a useful support herein, is a silica support treated with ammonium hexafluorosilicate and/or ammonium tetrafluoroborate fluorine compounds. Typically the fluorine concentration present on the support is in the range of from 0.1 to 25 wt %, alternately 0.19 to 19 wt %, alternately from 0.6 to 3.5 wt %, based upon the weight of the support.

In an embodiment of the invention, the catalyst system comprises fluorided silica, alkylalumoxane activator, and the bridged group 4 transition metal compound, where the fluorided support has not been calcined at a temperature of 400° C. or more.

The catalyst compound may be present on a support at 1 to 100 μmol/g supported catalyst, preferably 20-60 μmol/g supported catalyst.

This invention also relates to metallocene catalyst compositions comprising the reaction product of at least three components: (1) one or more bridged metallocenes having one tetrahydroindacenyl group; (2) one or more alkylalumoxane activators; and (3) one or more fluorided support compositions, where the fluorided support composition has not been calcined at 400° C. or more, preferably the fluorided support composition has been calcined at a temperature of 100° C. to 395° C., alternately 125° C. to 350° C., alternately 150° C. to 300° C.

Typically, the fluorided supports described herein are prepared by combining a solution of polar solvent (such as water) and fluorinating agent (such as SiF₄ or (NH₄)₂SiF₆) with a slurry of support (such as a toluene slurry of silica), then drying until it is free flowing, and optionally, calcining (typically at temperatures over 100° C. for at least 1 hour). The supports are then combined with activator(s) and catalyst compound (separately or together).

For more information on fluorided supports and methods to prepare them, please see U.S. Ser. No. 62/149,799, filed Apr. 20, 2015 (and all cases claiming priority to or the benefit of U.S. Ser. No. 62/149,799); U.S. Ser. No. 62/103,372, filed Jan. 14, 2015 (and all cases claiming priority to or the benefit of U.S. Ser. No. 62/103,372); and PCT/US2015/067582, filed Dec. 28, 2015 which are incorporated by reference herein.

Polymerization Processes

In embodiments herein, the invention relates to polymerization processes where monomer (such as ethylene), and optionally comonomer (such as hexene), are contacted with a catalyst system comprising the result of the combination of an activator, optional support (such as a fluorided support), and a tetrahydroindacene compound, as described above. The catalyst compound, optional support and activator may be combined in any order, and are combined typically prior to contacting with the monomer.

Monomers useful herein include substituted or unsubstituted C₂ to C₄₀ alpha olefins, preferably C₂ to C₂₀ alpha olefins, preferably C₂ to C₁₂ alpha olefins, preferably ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene and isomers thereof. In a preferred embodiment of the invention, the monomers comprises ethylene and optional comonomers comprising one or more C₃ to C₄₀ olefins, preferably C₄ to C₂₀ olefins, or preferably C₆ to C₁₂ olefins. The C₃ to C₄₀ olefin monomers may be linear, branched, or cyclic. The C₃ to C₄₀ cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may optionally include heteroatoms and/or one or more functional groups.

Exemplary C₃ to C₄₀ comonomers include propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof, and isomers thereof, preferably hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene, norbornadiene, 5-ethylidene-2-norbornene, and their respective homologs and derivatives.

In a preferred embodiment, one or more dienes are present in the polymer produced herein at up to 10 wt %, preferably at 0.00001 to 1.0 wt %, preferably 0.002 to 0.5 wt %, even more preferably 0.003 to 0.2 wt %, based upon the total weight of the composition. In some embodiments 500 ppm or less of diene is added to the polymerization, preferably 400 ppm or less, preferably or 300 ppm or less. In other embodiments at least 50 ppm of diene is added to the polymerization, or 100 ppm or more, or 150 ppm or more.

Preferred diolefin monomers useful in this invention include any hydrocarbon structure, preferably C₄ to C₃₀, having at least two unsaturated bonds, wherein at least two of the unsaturated bonds are readily incorporated into a polymer by either a stereospecific or a non-stereospecific catalyst(s). It is further preferred that the diolefin monomers be selected from alpha, omega-diene monomers (i.e., di-vinyl monomers). More preferably, the diolefin monomers are linear di-vinyl monomers, most preferably those containing from 4 to 30 carbon atoms. Examples of preferred dienes include butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene, pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, icosadiene, heneicosadiene, docosadiene, tricosadiene, tetracosadiene, pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene, nonacosadiene, triacontadiene, particularly preferred dienes include 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene, 1,13-tetradecadiene, and low molecular weight polybutadienes (Mw less than 1000 g/mol). Preferred cyclic dienes include cyclopentadiene, vinylnorbornene, norbornadiene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, divinylbenzene, dicyclopentadiene or higher ring containing diolefins with or without substituents at various ring positions.

In a particularly preferred embodiment, the process of the invention relates to the polymerization of ethylene and at least one comonomer having from 3 to 8 carbon atoms, preferably 4 to 8 carbon atoms. Particularly, the comonomers are propylene, butene-1, 4-methyl-pentene-1,3-methyl-pentene-1, hexene-1 and octene-1, the most preferred being hexene-1, butene-1 and octene-1.

Polymerization processes of this invention can be carried out in any manner known in the art. Any suspension, homogeneous, bulk, solution, slurry, or gas phase polymerization process known in the art can be used. Such processes can be run in a batch, semi-batch, or continuous mode. Gas phase polymerization processes and slurry processes are preferred. (A homogeneous polymerization process is defined to be a process where at least 90 wt % of the product is soluble in the reaction media.) A bulk homogeneous process is particularly preferred. (A bulk process is defined to be a process where monomer concentration in all feeds to the reactor is 70 vol % or more.) Alternately, no solvent or diluent is present or added in the reaction medium, (except for the small amounts used as the carrier for the catalyst system or other additives, or amounts typically found with the monomer; e.g., propane in propylene). In another embodiment, the process is a slurry process. As used herein the term “slurry polymerization process” means a polymerization process where a supported catalyst is employed and monomers are polymerized on the supported catalyst particles. At least 95 wt % of polymer products derived from the supported catalyst are in granular form as solid particles (not dissolved in the diluent).

Suitable diluents/solvents for polymerization include non-coordinating, inert liquids. Examples include straight and branched-chain hydrocarbons, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, such as can be found commercially (Isopar™); perhalogenated hydrocarbons, such as perfluorinated C₄₋₁₀ alkanes, chlorobenzene, and aromatic and alkylsubstituted aromatic compounds, such as benzene, toluene, mesitylene, and xylene. Suitable solvents also include liquid olefins which may act as monomers or comonomers including ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene, and mixtures thereof. In a preferred embodiment, aliphatic hydrocarbon solvents are used as the solvent, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof. In another embodiment, the solvent is not aromatic, preferably aromatics are present in the solvent at less than 1 wt %, preferably less than 0.5 wt %, preferably less than 0 wt % based upon the weight of the solvents.

In a preferred embodiment, the feed concentration of the monomers and comonomers for the polymerization is 60 vol % solvent or less, preferably 40 vol % or less, or preferably 20 vol % or less, based on the total volume of the feedstream. Preferably, the polymerization is run in a bulk process.

Preferred polymerizations can be run at any temperature and/or pressure suitable to obtain the desired polymers. Typical temperatures and/or pressures include a temperature in the range of from about 0° C. to about 300° C., preferably about 20° C. to about 200° C., preferably about 35° C. to about 150° C., preferably from about 40° C. to about 120° C., preferably from about 45° C. to about 80° C.; and at a pressure in the range of from about 0.35 MPa to about 16 MPa, preferably from about 0.45 MPa to about 13 MPa, or preferably from about 0.5 MPa to about 12 MPa.

In a typical polymerization, the run time of the reaction is up to 300 minutes, preferably in the range of from about 5 to 250 minutes, or preferably from about 10 to 120 minutes.

In some embodiments, hydrogen is present in the polymerization reactor at a partial pressure of 0.001 to 50 psig (0.007 to 345 kPa), preferably from 0.01 to 25 psig (0.07 to 172 kPa), more preferably 0.1 to 10 psig (0.7 to 70 kPa).

In an alternate embodiment, the activity of the catalyst is at least 800 gpolymer/gsupported catalyst/hour, preferably 1000 or more gpolymer/gsupported catalyst/hour, preferably 100 or more gpolymer/gsupported catalyst/hour, preferably 1600 or more gpolymer/gsupported catalyst/hour.

In a preferred embodiment, little or no scavenger is used in the process to produce the ethylene polymer. Preferably, scavenger (such as tri alkyl aluminum) is present at zero mol %, alternately the scavenger is present at a molar ratio of scavenger metal to transition metal of less than 100:1, preferably less than 50:1, preferably less than 15:1, preferably less than 10:1.

In a preferred embodiment, the polymerization: 1) is conducted at temperatures of 0° C. to 300° C. (preferably 25° C. to 150° C., preferably 40° C. to 120° C., preferably 45° C. to 80° C.); 2) is conducted at a pressure of atmospheric pressure to 16 MPa (preferably 0.35 to 14 MPa, preferably from 0.45 to 12 MPa, preferably from 0.5 to 6 MPa); 3) is conducted in an aliphatic hydrocarbon solvent (such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; preferably where aromatics are preferably present in the solvent at less than 1 wt %, preferably less than 0.5 wt %, preferably at 0 wt % based upon the weight of the solvents); 4) the polymerization preferably occurs in one reaction zone; and 5) optionally, hydrogen is present in the polymerization reactor at a partial pressure of 0.001 to 50 psig (0.007 to 345 kPa) (preferably from 0.01 to 25 psig (0.07 to 172 kPa), more preferably 0.1 to 10 psig (0.7 to 70 kPa)).

A “reaction zone” also referred to as a “polymerization zone” is a vessel where polymerization takes place, for example a batch reactor. When multiple reactors are used in either series or parallel configuration, each reactor is considered as a separate polymerization zone. For a multi-stage polymerization in both a batch reactor and a continuous reactor, each polymerization stage is considered as a separate polymerization zone. In a preferred embodiment, the polymerization occurs in one reaction zone.

Gas Phase Polymerization

Generally, in a fluidized gas bed process used for producing polymers, a gaseous stream containing one or more monomers is continuously cycled through a fluidized bed in the presence of a catalyst under reactive conditions. The gaseous stream is withdrawn from the fluidized bed and recycled back into the reactor. Simultaneously, polymer product is withdrawn from the reactor and fresh monomer is added to replace the polymerized monomer. (See for example U.S. Pat. Nos. 4,543,399; 4,588,790; 5,028,670; 5,317,036; 5,352,749; 5,405,922; 5,436,304; 5,453,471; 5,462,999; 5,616,661; and 5,668,228, all of which are fully incorporated herein by reference.)

Slurry Phase Polymerization

A slurry polymerization process generally operates between 1 to about 50 atmosphere pressure range (15 psi to 735 psi, 103 kPa to 5068 kPa) or even greater and temperatures in the range of 0° C. to about 120° C. In a slurry polymerization, a suspension of solid, particulate polymer is formed in a liquid polymerization diluent medium to which monomer and comonomers along with catalyst are added. The suspension including diluent is intermittently or continuously removed from the reactor where the volatile components are separated from the polymer and recycled, optionally after a distillation, to the reactor. The liquid diluent employed in the polymerization medium is typically an alkane having from 3 to 7 carbon atoms, preferably a branched alkane. The medium employed should be liquid under the conditions of polymerization and relatively inert. When a propane medium is used the process must be operated above the reaction diluent critical temperature and pressure. Preferably, a hexane or an isobutane medium is employed.

In an embodiment, a preferred polymerization technique useful in the invention is referred to as a particle form polymerization, or a slurry process where the temperature is kept below the temperature at which the polymer goes into solution. Such technique is well known in the art, and described in for instance U.S. Pat. No. 3,248,179 which is fully incorporated herein by reference. The preferred temperature in the particle form process is within the range of about 85° C. to about 110° C. Two preferred polymerization methods for the slurry process are those employing a loop reactor and those utilizing a plurality of stirred reactors in series, parallel, or combinations thereof. Non-limiting examples of slurry processes include continuous loop or stirred tank processes. Also, other examples of slurry processes are described in U.S. Pat. No. 4,613,484, which is herein fully incorporated by reference.

In another embodiment, the slurry process is carried out continuously in a loop reactor. The catalyst, as a slurry in isobutane or as a dry free flowing powder, is injected regularly to the reactor loop, which is itself filled with circulating slurry of growing polymer particles in a diluent of isobutane containing monomer and comonomer. Hydrogen, optionally, may be added as a molecular weight control. (In one embodiment 500 ppm or less of hydrogen is added, or 400 ppm or less or 300 ppm or less. In other embodiments at least 50 ppm of hydrogen is added, or 100 ppm or more, or 150 ppm or more.)

The reactor may be maintained at a pressure of 3620 kPa to 4309 kPa and at a temperature in the range of about 60° C. to about 104° C. depending on the desired polymer melting characteristics. Reaction heat is removed through the loop wall since much of the reactor is in the form of a double-jacketed pipe. The slurry is allowed to exit the reactor at regular intervals or continuously to a heated low pressure flash vessel, rotary dryer and a nitrogen purge column in sequence for removal of the isobutane diluent and all unreacted monomer and comonomers. The resulting hydrocarbon free powder is then compounded for use in various applications.

Other additives may also be used in the polymerization, as desired, such as one or more scavengers, promoters, modifiers, chain transfer agents (such as diethyl zinc), reducing agents, oxidizing agents, hydrogen, aluminum alkyls, or silanes.

Useful chain transfer agents are typically alkylalumoxanes, a compound represented by the formula AlR₃, ZnR₂ (where each R is, independently, a C₁-C₈ aliphatic radical, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl octyl or an isomer thereof) or a combination thereof, such as diethyl zinc, methylalumoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or a combination thereof.

Polyolefin Products

This invention also relates to compositions of matter produced by the methods described herein.

In a preferred embodiment, the process described herein produces ethylene homopolymers or ethylene copolymers, such as ethylene-alphaolefin (preferably C₃ to C₂₀) copolymers (such as ethylene-butene copolymers, ethylene-hexene and/or ethylene-octene copolymers) having: a Mw/Mn of greater than 1 to 4 (preferably greater than 1 to 3).

Likewise, the process of this invention produces ethylene copolymers. In a preferred embodiment, the copolymers produced herein have from 0 to 25 mol % (alternately from 0.5 to 20 mol %, alternately from 1 to 15 mol %, preferably from 3 to 10 mol %) of one or more C₃ to C₂₀ olefin comonomer (preferably C₃ to C₁₂ alpha-olefin, preferably propylene, butene, hexene, octene, decene, dodecene, preferably propylene, butene, hexene, octene).

In a preferred embodiment, the monomer is ethylene and the comonomer is hexene, preferably from 1 to 15 mol % hexene, alternately 1 to 10 mol %.

Typically, the polymers produced herein have an Mw of 5,000 to 1,000,000 g/mol (preferably 25,000 to 750,000 g/mol, preferably 50,000 to 500,000 g/mol), and/or an Mw/Mn of greater than 1 to 40 (alternately 1.2 to 20, alternately 1.3 to 10, alternately 1.4 to 5, 1.5 to 4, alternately 1.5 to 3).

In a preferred embodiment, the polymer produced herein has a unimodal or multimodal molecular weight distribution as determined by Gel Permeation Chromatography (GPC). By “unimodal” is meant that the GPC trace has one peak or inflection point. By “multimodal” is meant that the GPC trace has at least two peaks or inflection points. An inflection point is that point where the second derivative of the curve changes in sign (e.g., from negative to positive or vice versus).

Unless otherwise indicated Mw, Mn and Mw/Mn are determined by using a High Temperature Gel Permeation Chromatography (Agilent PL-220), equipped with three in-line detectors, a differential refractive index detector (DRI), a light scattering (LS) detector, and a viscometer. Experimental details, including detector calibration, are described in: T. Sun, P. Brant, R. R. Chance, and W. W. Graessley, Macromolecules, Volume 34, Number 19, pp. 6812-6820, (2001) and references therein. Three Agilent PLgel 10 μm Mixed-B LS columns are used. The nominal flow rate is 0.5 mL/min, and the nominal injection volume is 300 μL. The various transfer lines, columns, viscometer and differential refractometer (the DRI detector) are contained in an oven maintained at 145° C. Solvent for the experiment is prepared by dissolving 6 grams of butylated hydroxytoluene as an antioxidant in 4 liters of Aldrich reagent grade 1,2,4-trichlorobenzene (TCB). The TCB mixture is then filtered through a 0.1 μm Teflon filter. The TCB is then degassed with an online degasser before entering the GPC-3D. Polymer solutions are prepared by placing dry polymer in a glass container, adding the desired amount of TCB, then heating the mixture at 160° C. with continuous shaking for about 2 hours. All quantities are measured gravimetrically. The TCB densities used to express the polymer concentration in mass/volume units are 1.463 g/ml at room temperature and 1.284 g/ml at 145° C. The injection concentration is from 0.5 to 2.0 mg/ml, with lower concentrations being used for higher molecular weight samples. Prior to running each sample the DRI detector and the viscometer are purged. Flow rate in the apparatus is then increased to 0.5 ml/minute, and the DRI is allowed to stabilize for 8 hours before injecting the first sample. The LS laser is turned on at least 1 to 1.5 hours before running the samples. The concentration, c, at each point in the chromatogram is calculated from the baseline-subtracted DRI signal, I_(DRI), using the following equation: c=K _(DRI) I _(DRI)/(dn/dc) where K_(DRI) is a constant determined by calibrating the DRI, and (dn/dc) is the refractive index increment for the system. The refractive index, n=1.500 for TCB at 145° C. and λ=690 nm. Units on parameters throughout this description of the GPC-3D method are such that concentration is expressed in g/cm³, molecular weight is expressed in g/mole, and intrinsic viscosity is expressed in dL/g.

The LS detector is a Wyatt Technology High Temperature DAWN HELEOS. The molecular weight, M, at each point in the chromatogram is determined by analyzing the LS output using the Zimm model for static light scattering (M. B. Huglin, LIGHT SCATTERING FROM POLYMER SOLUTIONS, Academic Press, 1971):

$\frac{K_{o}c}{\Delta{R(\theta)}} = {\frac{1}{M{P(\theta)}} + {2A_{2}c}}$

Here, ΔR(θ) is the measured excess Rayleigh scattering intensity at scattering angle θ, c is the polymer concentration determined from the DRI analysis, A₂ is the second virial coefficient. P(θ) is the form factor for a monodisperse random coil, and K_(o) is the optical constant for the system:

$K_{o} = \frac{4\pi^{2}{n^{2}\left( {d{n/d}c} \right)}^{2}}{\lambda^{4}N_{A}}$ where N_(A) is Avogadro's number, and (dn/dc) is the refractive index increment for the system, which take the same value as the one obtained from DRI method. The refractive index, n=1.500 for TCB at 145° C. and λ=690 nm.

A high temperature Viscotek Corporation viscometer, which has four capillaries arranged in a Wheatstone bridge configuration with two pressure transducers, is used to determine specific viscosity. One transducer measures the total pressure drop across the detector, and the other, positioned between the two sides of the bridge, measures a differential pressure. The specific viscosity, η_(s), for the solution flowing through the viscometer is calculated from their outputs. The intrinsic viscosity, [η], at each point in the chromatogram is calculated from the following equation: η_(s) =c[η]+0.3(c[η])² where c is concentration and was determined from the DRI output. All molecular weights are weight average unless otherwise noted. All molecular weights are reported in g/mol unless otherwise noted.

In a preferred embodiment, the polymer produced herein has a composition distribution breadth index (CDBI) of 50% or more, preferably 60% or more, preferably 70% or more. CDBI is a measure of the composition distribution of monomer within the polymer chains and is measured by the procedure described in PCT publication WO 93/03093, published Feb. 18, 1993, specifically columns 7 and 8 as well as in Wild et al, J. Poly. Sci., Poly. Phys. Ed., Vol. 20, p. 441 (1982) and U.S. Pat. No. 5,008,204, including that fractions having a weight average molecular weight (Mw) below 15,000 are ignored when determining CDBI.

In another embodiment, the polymer produced herein has two peaks in the TREF measurement (see below). Two peaks in the TREF measurement as used in this specification and the appended claims means the presence of two distinct normalized ELS (evaporation mass light scattering) response peaks in a graph of normalized ELS response (vertical or y axis) versus elution temperature (horizontal or x axis with temperature increasing from left to right) using the TREF method below. A “peak” in this context means where the general slope of the graph changes from positive to negative with increasing temperature. Between the two peaks is a local minimum in which the general slope of the graph changes from negative to positive with increasing temperature. “General trend” of the graph is intended to exclude the multiple local minimums and maximums that can occur in intervals of 2° C. or less. Preferably, the two distinct peaks are at least 3° C. apart, more preferably at least 4° C. apart, even more preferably at least 5° C. apart. Additionally, both of the distinct peaks occur at a temperature on the graph above 20° C. and below 120° C. where the elution temperature is run to 0° C. or lower. This limitation avoids confusion with the apparent peak on the graph at low temperature caused by material that remains soluble at the lowest elution temperature. Two peaks on such a graph indicates a bi-modal composition distribution (CD). Bimodal CD may also be determined by other methods known to those skilled in the art. One such alternate method for TREF measurement then can be used if the above method does not show two peaks is disclosed in B. Monrabal, “Crystallization Analysis Fractionation: A New Technique for the Analysis of Branching Distribution in Polyolefins,” Journal of Applied Polymer Science, Vol. 52, 491-499 (1994).

TREF Method

Temperature Rising Elution Fractionation (TREF) analysis is done using a CRYSTAF-TREF 200+ instrument from Polymer Char, S. A., Valencia, Spain. The principles of TREF analysis and a general description of the particular apparatus to be used are given in the article Monrabal, B.; del Hierro, P. Anal. Bioanal. Chem., 2011, 399, 1557. FIG. 3 of the article is an appropriate schematic of the particular apparatus used; however, the connections to the 6-port valve shown in FIG. 3 differ from the apparatus to be used in that the tubing connected to the 11-o'clock port is connected to the 9-o'clock port and the tubing connected to the 9-o'clock port is connected to the 11-o'clock port. Pertinent details of the analysis method and features of the apparatus to be used are as follows.

1,2-Dichlorobenzene (ODCB) solvent stabilized with approximately 380 ppm of 2,6-bis(1,1-dimethylethyl)-4-methylphenol (butylated hydroxytoluene) is used for preparing the sample solution and for elution. The sample to be analyzed (approximately 25 mg but as low as approximately 10 mg) is dissolved in ODCB (25 ml metered at ambient temperature) by stirring at 150° C. for 60 min. A small volume (0.5 ml) of the solution is introduced into a column (15-cm long by ⅜″ o.d.) packed with an inert support (of stainless steel balls) at 150° C., and the column temperature is stabilized at 140° C. for 45 min. The sample volume is then allowed to crystallize in the column by reducing the temperature to 30° C. at a cooling rate of 1° C./min. The column is kept at 30° C. for 15 min before injecting the ODCB flow (1 ml/min) into the column for 10 min to elute and measure the polymer that did not crystallize (soluble fraction). The infrared detector used (Polymer Char IR4) generates an absorbance signal that is proportional to the concentration of polymer in the eluting flow. A complete TREF curve is then generated by increasing the temperature of the column from 30 to 140° C. at a rate of 2° C./min while maintaining the ODCB flow at 1 ml/min to elute and measure the dissolving polymer.

Blends

In another embodiment, the polymer produced herein is combined with one or more additional polymers prior to being formed into a film, molded part or other article. Other useful polymers include polyethylene, isotactic polypropylene, highly isotactic polypropylene, syndiotactic polypropylene, random copolymer of propylene and ethylene, and/or butene, and/or hexene, polybutene, ethylene vinyl acetate, LDPE, LLDPE, HDPE, ethylene vinyl acetate, ethylene methyl acrylate, copolymers of acrylic acid, polymethylmethacrylate or any other polymers polymerizable by a high-pressure free radical process, polyvinylchloride, polybutene-1, isotactic polybutene, ABS resins, ethylene-propylene rubber (EPR), vulcanized EPR, EPDM, block copolymer, styrenic block copolymers, polyamides, polycarbonates, PET resins, cross linked polyethylene, copolymers of ethylene and vinyl alcohol (EVOH), polymers of aromatic monomers such as polystyrene, poly-1 esters, polyacetal, polyvinylidine fluoride, polyethylene glycols, and/or polyisobutylene.

In a preferred embodiment, the polymer (preferably the polyethylene produced herein) is present in the above blends, at from 10 to 99 wt %, based upon the weight of the polymers in the blend, preferably 20 to 95 wt %, even more preferably at least 30 to 90 wt %, even more preferably at least 40 to 90 wt %, even more preferably at least 50 to 90 wt %, even more preferably at least 60 to 90 wt %, even more preferably at least 70 to 90 wt %.

Additionally, additives may be included in the blend, in one or more components of the blend, and/or in a product formed from the blend, such as a film, as desired. Such additives are well known in the art, and can include, for example: fillers; antioxidants (e.g., hindered phenolics such as IRGANOX™ 1010 or IRGANOX™ 1076 available from Ciba-Geigy); phosphites (e.g., IRGAFOS™ 168 available from Ciba-Geigy); anti-cling additives; tackifiers, such as polybutenes, terpene resins, aliphatic and aromatic hydrocarbon resins, alkali metal and glycerol stearates, and hydrogenated rosins; UV stabilizers; heat stabilizers; anti-blocking agents; release agents; anti-static agents; pigments; colorants; dyes; waxes; silica; fillers; talc; and the like.

Films

Specifically, any of the foregoing polymers, such as the foregoing ethylene copolymers or blends thereof, may be used in a variety of end-use applications. Such applications include, for example, mono- or multi-layer blown, extruded, and/or shrink films. These films may be formed by any number of well known extrusion or coextrusion techniques, such as a blown bubble film processing technique, wherein the composition can be extruded in a molten state through an annular die and then expanded to form a uni-axial or biaxial orientation melt prior to being cooled to form a tubular, blown film, which can then be axially slit and unfolded to form a flat film. Films may be subsequently unoriented, uniaxially oriented, or biaxially oriented to the same or different extents. One or more of the layers of the film may be oriented in the transverse and/or longitudinal directions to the same or different extents. The uniaxially orientation can be accomplished using typical cold drawing or hot drawing methods. Biaxial orientation can be accomplished using tenter frame equipment or a double bubble processes and may occur before or after the individual layers are brought together. For example, a polyethylene layer can be extrusion coated or laminated onto an oriented polypropylene layer or the polyethylene and polypropylene can be coextruded together into a film then oriented. Likewise, oriented polypropylene could be laminated to oriented polyethylene or oriented polyethylene could be coated onto polypropylene then optionally the combination could be oriented even further. Typically the films are oriented in the Machine Direction (MD) at a ratio of up to 15, preferably between 5 and 7, and in the Transverse Direction (TD) at a ratio of up to 15, preferably 7 to 9. However, in another embodiment, the film is oriented to the same extent in both the MD and TD directions.

The films may vary in thickness depending on the intended application; however, films of a thickness from 1 to 50 μm are usually suitable. Films intended for packaging are usually from 10 to 50 μm thick. The thickness of the sealing layer is typically 0.2 to 50 μm. There may be a sealing layer on both the inner and outer surfaces of the film or the sealing layer may be present on only the inner or the outer surface.

In another embodiment, one or more layers may be modified by corona treatment, electron beam irradiation, gamma irradiation, flame treatment, or microwave. In a preferred embodiment, one or both of the surface layers is modified by corona treatment.

EXPERIMENTAL

Room temperature is 23° C. unless otherwise noted.

The inventive pre-catalysts are illustrated below:

Starting Reagents: Diethyl malonate (Acros), diethyl methylmalonate (Acros), iodomethane (Acros), iodoethane (Acros), bromoethane (Merck), 1,2-bis(bromomethyl)benzene (Aldrich), methylmagnesium bromide solution in ether (Aldrich), n-butyllithium solution in hexanes (Chemetal), sodium borohydride (Aldrich), TsOH (Aldrich), ZrCl₄(THF)₂ (Aldrich), HfCl₄(THF)₂ (Aldrich), CuCN (Merck), sodium metal (Merck), Na₂CO₃ (Merck), K₂CO₃ (Merck), AlCl₃ (Merck), thionyl chloride (Merck), silica gel 60, 40-63 um (Merck), potassium tert-butoxide (Acros), hydrazine hydrate (Acros), 12 M HCl (Merck), KOH (Merck), 96% ethanol (Merck), anhydrous ethanol (Merck), methanol (Merck), ethyleneglycol (Acros), dichloromethane (Merck), benzene (Merck), and CDCl₃ (Deutero GmbH) were used as received. Dichlorodimethylsilane (Merck) and 1,2-dichlorotetramethyldisilane (Aldrich) were distilled before use. THF and diethyl ether (both Merck) for organometallic synthesis were distilled over sodium benzophenone ketyl. Toluene, n-hexane, and n-octane (all Merck) for organometallic synthesis as well as CDCl₃ and CD₂Cl₂ (both Deutero GmbH) for NMR analysis of air- and moisture-sensitive compounds were dried over molecular sieves 4 A (Acros) and flashed by dry argon before use. 1,1-Dichlorosilolane was obtained from 1,4-dibromobutane (Acros), magnesium turnings (Acros), and silicon tetrachloride (Merck) as described in [Mironov, V. F.; Nepomnina, V. V. Izv. Akad. Nauk SSSR, Ser. Khim., 1959, 1231].

Tetrahydro-as-Indacene Ligand Synthesis:

Example 1: Synthesis of 2,2,7-Trimethyl-1,2,3,6-tetrahydro-as-indacene 2-Methyl-3-(2-methyl-1-oxo-2,3-dihydro-1H-inden-4-yl)propanoic Acid

In a three-necked round-bottom flask, 46.0 g (2.0 mol) of sodium metal was dissolved in 1100 ml of dry ethanol. To the resulting solution 348.5 g (2.0 mol) of diethyl methylmalonate was added. This mixture was stirred for 15 min., then 264 g (1.0 mol) of 1,2-bis(bromomethyl)benzene was added in several portions to maintain a gentle reflux. This mixture was refluxed for an additional 3 h and then cooled to room temperature. A solution of 411 g of KOH in 1200 ml of water was added. The resulting mixture was refluxed for 6 h to saponificate the ester formed. Ethanol and water were distilled off until temperature reached 95° C., and 4 L of water and then 12 M HCl (to pH 1) were added to the residue. The precipitated acid was filtered off, washed with 3×500 ml of cold water, and then decarboxylated at 200° C. to give 3,3′-(1,2-phenylene)bis(2-methylpropanoic acid).

¹H NMR (CDCl₃): δ 11.4 (bs, 2H), 7.16 (s, 4H), 3.20-3.11 (m, 2H), 2.79-2.63 (m, 4H), 1.2 (d, 6H, J=6.6 Hz). ¹³C{¹H} NMR (CDCl₃): δ 182.78, 137.29, 129.92, 129.85, 126.61, 40.66, 40.62, 35.66, 16.63, 16.57.

A mixture of this acid and 511 ml of thionyl chloride was stirred at room temperature for 24 h. An excess of thionyl chloride was distilled off, the residue was dried in vacuum to give crude 3,3′-(1,2-phenylene)bis(2-methylpropanoyl chloride) which was further used without an additional purification. To a stirred suspension of 166.5 g (1.25 mol) of AlCl₃ in 1200 ml of dichloromethane cooled to 0° C., a solution of 3,3′-(1,2-phenylene)bis(2-methylpropanoyl chloride) in 200 ml of dichloromethane was added dropwise with vigorous stirring. This mixture was stirred overnight at room temperature and then poured on 2 kg of ice. The organic layer was separated, and the aqueous layer was additionally extracted with 3×250 ml of dichloromethane. The combined organic extract was evaporated to dryness, and the residue was dissolved in a cold solution of 100 g KOH in 1200 ml water. The obtained mixture was extracted with 2×200 ml of ether, then, acidified with 12 M HCl to pH 1. The resulting mixture was extracted with 3×400 ml of dichloromethane. The combined organic extract was passed through a short pad of silica gel 60 (40-63 um), and the obtained filtrate was evaporated to dryness to give 147.5 g (63.5% yield) of a mixture of diastereomers of 2-methyl-3-(2-methyl-1-oxo-2,3-dihydro-1H-inden-4-yl)propanoic acid, a yellow oil which was further used without an additional purification.

¹H NMR (CDCl₃): δ 10.2 (br.s, 1H), 7.65 (d, J=7.6 Hz, 1H), 7.43 (d, J=7.6 Hz, 1H), 7.33 (t, J=7.6 Hz, 1H), 3.45-3.30 (m, 1H), 3.19-3.08 (m, 1H), 2.90-2.79 (m, 1H), 2.79-2.59 (m, 3H), 1.32 (d, J=7.3 Hz, 3H), 1.31 (d, J=7.3 Hz, 3H), 1.25 (d, J=6.8 Hz, 3H). ¹³C{¹H} NMR (CDCl₃): δ 209.79, 181.54, 181.50, 152.27, 136.86, 136.46, 134.93, 127.76, 122.35, 41.87, 39.84, 35.23, 33.60, 16.86, 16.29.

Methyl 2-methyl-3-(2-methyl-1-oxo-2,3-dihydro-1H-inden-4-yl)propanoate

To a solution of 408 g (1.76 mol) of 2-methyl-3-(2-methyl-1-oxo-2,3-dihydro-1H-inden-4-yl)propanoic acid in 1400 ml of methanol cooled to 0° C. 154 ml (251 g, 2.11 mol, 1.2 equiv) of thionyl chloride was added dropwise for 2 h. This mixture was allowed to reach room temperature and then refluxed for 0.5 h. The obtained mixture was evaporated on Rotavapor, the residue was dissolved in 1000 ml of dichloromethane. This solution was washed with aqueous K₂CO₃, dried over K₂CO₃, and then evaporated to dryness to give a yellowish oil. This oil was rectificated in vacuum to give 335 g (78% yield) of a mixture of two diastereomers of methyl 2-methyl-3-(2-methyl-1-oxo-2,3-dihydro-1H-inden-4-yl)propanoate as a yellowish oil, b.p. 162° C./3 mm Hg.

Anal. calc. for C₁₅H₁₈O₃: C, 73.15; H, 7.37. Found: C, 73.56; H, 7.61.

¹H NMR (CDCl₃): δ 7.62 (d, J=7.6 Hz, 1H), 7.39 (d, J=7.6 Hz, 1H), 7.31 (‘t’, J=7.6 Hz, 1H), 3.63 (s, 3H), 3.42-3.32 (m, 1H), 3.12-3.07 (m, 1H), 2.86-2.61 (m, 4H), 1.32 (2d, J=6.6 Hz, 3H), 1.21 (2d, J=6.6 Hz, 3H). ¹³C{¹H} NMR (CDCl₃): δ 209.37, 176.14, 152.12, 137.15, 136.52, 134.81, 127.67, 122.20, 51.66, 41.92, 41.88, 40.00, 39.97, 35.64, 33.62, 17.11, 17.08, 16.31, 16.27.

3-(2,2-Dimethyl-1-oxo-2,3-dihydro-1H-inden-4-yl)-2-methylpropanoic Acid

To a mixture of 335 g (1.36 mol) of methyl 2-methyl-3-(2-methyl-1-oxo-2,3-dihydro-1H-inden-4-yl)propanoate and 232 g (1.63 mol, 1.2 equiv) of methyl iodide cooled to 0° C., a solution of 183 g (1.63 mol, 1.2 equiv) of ^(t)BuOK in 1200 ml of THF was added dropwise for 4 h, and the reaction mixture was then stirred overnight at room temperature. Further on, this mixture was evaporated on Rotavapor. To the residue a solution of 150 g of KOH in a mixture of 800 ml of water and 250 ml of methanol was added. The resulting mixture was refluxed for 4 h to saponificate the ester. Further on, methanol and water were distilled off until temperature reached 95° C., and 3 L of water and then 12 M HCl (to pH 1) were added to the residue. Crude product was extracted with 500 ml of dichloromethane. The aqueous phase was additionally extracted with 3×250 ml of dichloromethane. The combined organic extract was evaporated to dryness, and the residue was re-crystallized from a ca. 5:1 (vol.) mixture of hexane and benzene to give 296 g (88% yield) of 3-(2,2-dimethyl-1-oxo-2,3-dihydro-1H-inden-4-yl)-2-methylpropanoic acid.

¹H NMR (CDCl₃): δ 10.5 (br.s, 1H), 7.66 (d, J=7.6 Hz, 1H), 7.44 (d, J=7.6 Hz, 1H), 7.34 (‘t’, J=7.6 Hz, 1H), 3.12 (dd, J=13.6 Hz, J=6.8 Hz, 1H), 3.03-2.89 (m, 2H), 2.83 (m, 1H), 2.72 (dd, J=13.6 Hz, J=7.8 Hz, 1H), 1.25 (d, J=6.8 Hz, 3H), 1.25 (s, 3H), 1.24 (s, 3H). ¹³C{¹H} NMR (CDCl₃): δ 211.67, 181.80, 150.98, 136.87, 135.44, 135.06, 127.84, 122.83, 45.45, 41.54, 39.92, 35.22, 25.27, 16.86.

3-(2,2-Dimethyl-2,3-dihydro-1H-inden-4-yl)-2-methylpropionyl Chloride

To a solution of 296 g (1.2 mol) of 3-(2,2-dimethyl-1-oxo-2,3-dihydro-1H-inden-4-yl)-2-methylpropanoic acid in a mixture of 260 g (˜4.6 mol) of KOH and 2500 ml of ethylene glycol, 252 ml of hydrazine hydrate was added. The reaction mixture was refluxed for 5 h. Then, the reflux condenser was replaced by a Claisen distillation head with a Liebig condenser, and a mixture of water, hydrazine hydrate, and ethylene glycol was slowly distilled off until the distillation temperature reached 195° C. The residue was then allowed to cool to room temperature, poured into 5 L of water, acidified with 12 M HCl to pH=1, and crude product was extracted with 1 liter of dichloromethane. The aqueous phase was additionally extracted with 2×500 ml of dichloromethane. The combined organic extract was washed with 1 L of water and evaporated to dryness to give 3-(2,2-dimethyl-2,3-dihydro-1H-inden-4-yl)-2-methylpropanoic acid as a red viscous oil.

¹H NMR (CDCl₃): δ 11.0 (br.s, 1H), 7.1-7.0 (m, 2H), 6.94 (d, J=7.1 Hz, 1H), 3.02 (dd, J=13.5 Hz, J=6.2 Hz, 1H), 2.79-2.64 (m, 5H), 2.59 (dd, J=13.5 Hz, J=8.4 Hz, 1H), 1.17 (d, J=7.1 Hz, 3H), 1.14 (s, 6H). ¹³C{¹H} NMR (CDCl₃): δ 182.86, 143.75, 142.33, 135.09, 126.71, 126.27, 122.92, 47.86, 46.18, 40.27, 39.71, 36.76, 28.83, 16.49.

A mixture of the above-obtained acid and 307 ml (501 g, 4.21 mol) of thionyl chloride was stirred for 24 h at room temperature. An excess of thionyl chloride was distilled off, the residue was distilled in vacuum to give 270 g [90% yield from 3-(2,2-dimethyl-1-oxo-2,3-dihydro-1H-inden-4-yl)-2-methylpropanoic acid] of 3-(2,2-dimethyl-2,3-dihydro-1H-inden-4-yl)-2-methylpropionyl chloride, b.p. 138-150° C./2 mm Hg.

¹H NMR (CDCl₃): δ 7.15-7.0 (m, 2H), 6.93 (d, J=7.1 Hz, 1H), 3.19-3.06 (m, 2H), 2.77-2.6 (m, 5H), 1.27 (d, J=7.07 Hz, 3H), 1.16 (s, 3H), 1.15 (s, 3H). ¹³C{¹H} NMR (CDCl₃): δ 177.19, 144.04, 142.31, 133.64, 126.75, 126.49, 123.39, 52.25, 47.80, 46.19, 39.84, 36.71, 28.80, 16.59.

2,7,7-Trimethyl-1,6,7,8-tetrahydro-as-indacen-3(2H)-one

To a suspension of 173 g (1.29 mol, 1.2 eq.) of AlCl₃ in 1000 ml of dichloromethane cooled to 0° C., a solution of 270 g (1.08 mol) of 3-(2,2-dimethyl-2,3-dihydro-1H-inden-4-yl)-2-methylpropionyl chloride in 2500 ml of dichloromethane was added for 1 h. The cooling bath was then removed, and the solution was stirred overnight at room temperature. The reaction mixture was poured into 2 kg of crushed ice, the organic phase was separated, and the aqueous phase was extracted by 3×500 ml of dichloromethane. The combined organic extract was washed with aqueous K₂CO₃, dried over K₂CO₃, passed through a short pad of silica gel 60 (40-63 um), and the elute was evaporated to dryness. The residue was rectificated in vacuum to give 223 g (97% yield) of 2,7,7-trimethyl-1,6,7,8-tetrahydro-as-indacen-3(2H)-one as a yellowish oil which crystallizes at room temperature, b.p. 137° C.-138° C./1 mm Hg. Anal. calc. for C₁₅H₁₈O: C, 84.07; H, 8.47. Found: C, 84.42; H, 8.69.

¹H NMR (CDCl₃): δ 7.57 (d, J=7.6 Hz, 1H), 7.18 (d, J=7.6 Hz, 1H), 3.24 (dd, J=17.2 Hz, J=7.8 Hz, 1H), 2.80 (s, 2H), 2.71 (s, 2H), 2.75-2.65 (m, 1H), 2.56 (dd, J=17.2 Hz, J=3.5 Hz, 1H), 1.31 (d, J=7.6 Hz, 3H), 1.20 (s, 3H), 1.18 (s, 3H). ¹³C{¹H} NMR (CDCl₃): δ 209.31, 151.10, 149.82, 140.60, 134.81, 123.97, 122.22, 48.12, 44.86, 42.13, 40.34, 33.48, 28.90, 16.46.

2,2,7-Trimethyl-1,2,3,6-tetrahydro-as-indacene (Illustrated as the 2,2,7-trimethyl-1,2,3,8-tetrahydro-as-indacene Isomer)

To a solution of 94.9 g (442.8 mmol) of 2,7,7-trimethyl-1,6,7,8-tetrahydro-as-indacen-3(2H)-one in 440 ml of THF cooled to 5° C. 25.1 g (664 mmol) of NaBH₄ was added. Further on, 220 ml of methanol was added dropwise to this vigorously stirred mixture for ca. 5 h at 5° C. The resulting mixture was stirred for 3 h at room temperature, then evaporated to dryness, and the residue was partitioned between 500 ml of dichloromethane and 500 ml of 2 M HCl. The organic layer was separated, and the aqueous layer was additionally extracted with 100 ml of dichloromethane. The combined organic extract was evaporated to dryness. To a solution of the residue in 900 ml of toluene 1 g of TsOH was added, and this mixture was refluxed with Dean-Stark head for 20 min., then cooled to room temperature using a water bath. The resulting solution was washed by 10% Na₂CO₃. The organic layer was separated, and the aqueous layer was extracted with 2×100 ml of dichloromethane. The combined organic extract was dried over K₂CO₃ and then passed through a short pad of silica gel 60 (40-63 um). The silica gel pad was additionally washed by 100 ml of dichloromethane. The combined organic elute was evaporated to dryness. Crude product was rectificated in vacuum to give 79.6 g (91% yield) of 2,2,7-trimethyl-1,2,3,6-tetrahydro-as-indacene as yellowish oil which crystallizes rapidly at room temperature, b.p. 119° C.-125° C./2 mm Hg. Anal. calc. for C₁₅H₁₈: C, 90.85; H, 9.15. Found: C, 90.76; H, 9.24.

¹H NMR (CDCl₃): δ 7.06-6.99 (m, 2H), 6.45 (br.s, 1H), 3.13 (s, 2H), 2.74 (s, 2H), 2.67 (s, 2H), 2.13 (s, 3H), 1.16 (s, 6H). ¹³C{¹H} NMR (CDCl₃): δ 144.40, 144.10, 139.37, 139.08, 138.18, 127.32, 122.41, 117.62, 47.66, 45.87, 41.19, 40.26, 29.09, 16.77.

Example 2: Synthesis of 2,2,7-Triethyl-1,2,3,6-tetrahydro-as-indacene 2-[(2-Ethyl-1-oxo-2,3-dihydro-1H-inden-4-yl)methyl]butanoic Acid

In a three-necked round-bottom flask, 36.0 g (1.57 mol) of sodium metal was dissolved in 700 ml of dry ethanol. To the resulting solution, 500 g (3.12 mol) of diethyl malonate was added. This mixture was stirred for 15 min., then 206 g (0.78 mol) of 1,2-bis(bromomethyl)benzene was added in several portions to maintain a gentle reflux. This mixture was refluxed for an additional 3 h and then cooled to room temperature. Ethanol was distilled off, and 1000 ml of water was added to the residue at room temperature. The separated oil was extracted with 1000 ml of dichloromethane. The extract was evaporated on a Rotavapor, and an excess of diethyl malonate as well as by-product, i.e. diethyl 1,3-dihydro-2H-indene-2,2-dicarboxylate, were distilled off in vacuum (<180° C./3 mm Hg). The residual tetraethyl 2,2′-[1,2-phenylenedi(methylene)]dimalonate was further used without an additional purification.

¹H NMR (CDCl₃): δ 7.17-7.11 (m), 4.16 (q, J=7.3 Hz), 4.15 (q, J=7.3 Hz), 3.69 (t, J=7.8 Hz), 3.29 (d, J=7.8 Hz), 1.20 (t, J=7.3 Hz).

To a solution of sodium ethoxide (obtained from 33.4 g (1.45 mol) of sodium metal and 750 ml of dry ethanol), tetraethyl 2,2′-[1,2-phenylenedi(methylene)]dimalonate (as prepared above) was added. The formed mixture was stirred for 15 min., and then 158 g (1.45 mol) of bromoethane was added. The resulting mixture was refluxed for 7 h and then cooled to room temperature. A solution of 312 g of KOH in 850 ml of water was added. This mixture was refluxed for 5 h to saponificate the ester. Ethanol and water were distilled off until vapor temperature reached 95° C., and 3000 ml of water and then 12 M HCl (to pH˜1) were added to the residue. Crude 2,2′-[1,2-phenylenedi(methylene)]bis(ethylmalonic acid) was extracted with ether, the extract was evaporated to dryness, and the formed solid material was then decarboxylated at 160° C.-180° C. to form 2,2′-[1,2-phenylenedi(methylene)]dibutanoic acid as a yellowish oil which was further used without an additional purification.

¹H NMR (CDCl₃): δ 11.6 (br.s, 2H), 7.19-7.07 (m, 4H), 3.09-2.94 (m, 2H), 2.85-2.69 (m, 2H), 2.68-2.55 (m, 2H), 1.77-1.52 (m, 4H), 0.96 (t, J=7.4 Hz, 6H).

A mixture of this acid and 240 ml (3.31 mol) of thionyl chloride was stirred for 24 h at room temperature. After evaporation of an excess of thionyl chloride, the residue was dried in vacuum to give crude 2,2′-[1,2-phenylenedi(methylene)]dibutanoyl chloride which was further used without an additional purification. To a stirred suspension of 80.0 g (0.6 mol) of AlCl₃ in 600 ml of dichloromethane cooled to 0° C., a solution of 2,2′-[1,2-phenylenedi(methylene)]dibutanoyl chloride in 200 ml of dichloromethane was added dropwise. This mixture was stirred overnight at room temperature and then poured on 1000 g of ice. The organic layer was separated, and the aqueous layer was additionally extracted with 350 ml of dichloromethane. The combined organic extract was evaporated to dryness, and the residue was dissolved in a cold solution of 54 g KOH in 700 ml water. The obtained solution was extracted with 2×200 of ether, then acidified with 12 M HCl to pH 1. The formed mixture was extracted with 3×250 ml of dichloromethane. The combined organic extract was passed through a short pad of silica gel 60 (40-63 um), and the obtained filtrate was evaporated to dryness to give 136.5 g [67% yield from 1,2-bis(bromomethyl)benzene] of 2-[(2-ethyl-1-oxo-2,3-dihydro-1H-inden-4-yl)methyl]butanoic acid as a yellow oil which was further used without an additional purification.

¹H NMR (CDCl₃): δ 9.1 (br.s, 1H), 7.61 (d, J=7.6 Hz, 1H), 7.43 (d, J=7.3 Hz, 1H), 7.34-7.26 (m, 1H), 3.40-3.19 (m, 1H), 3.12-2.96 (m, 1H), 2.92-2.53 (m, 4H), 2.05-1.86 (m, 1H), 1.84-1.42 (m, 3H), 1.10-0.86 (m, 6H).

Ethyl 2-[(2-ethyl-1-oxo-2,3-dihydro-1H-inden-4-yl)methyl]butanoate

To a solution of 136.5 g (524 mmol) of 2-[(2-ethyl-1-oxo-2,3-dihydro-1H-inden-4-yl)methyl]butanoic acid in 400 ml of ethanol cooled to 0° C., 46 ml (634 mmol, 1.2 equiv) of thionyl chloride was added dropwise over 1 h. This mixture was allowed to reach room temperature and then refluxed for 2 h. The obtained mixture was evaporated on a Rotavapor, the residue was dissolved in 500 ml of dichloromethane. This solution was washed with aqueous K₂CO₃, dried over K₂CO₃, and then evaporated to dryness to give a yellow oil. This oil was rectificated in vacuum to give 87.0 g (56% yield) of a mixture of two diastereomers of ethyl 2-[(2-ethyl-1-oxo-2,3-dihydro-1H-inden-4-yl)methyl]butanoate as a yellowish oil, b.p. 195° C.-210° C./7 mm Hg.

Anal. calc. for C₁₈H₂₄O₃: C, 74.97; H, 8.39. Found: C, 75.16; H, 8.50.

¹H NMR (CDCl₃): δ 7.61 (d, J=7.6 Hz, 1H), 7.40 (d, J=7.3 Hz, 1H), 7.33-7.27 (m, 1H), 4.10-4.00 (m, 2H), 3.37-3.21 (m, 1H), 3.05-2.95 (m, 1H), 2.88-2.56 (m, 4H), 2.06-1.91 (m, 1H), 1.82-1.47 (m, 3H), 1.13 and 1.11 (two t, J=7.3 Hz, 3H), 1.03 (t, J=7.3 Hz, 3H), 0.97 (t, J=7.3 Hz, 3H). ¹³C{¹H} NMR (CDCl₃): δ 208.91, 175.10, 152.42, 137.19, 136.95, 134.66, 127.48, 121.84, 60.14, 48.57, 48.54, 47.61, 47.51, 34.08, 34.05, 30.88, 30.84, 25.56, 25.51, 24.45, 24.37, 14.08, 14.06, 11.65, 11.49.

2-[(2,2-Diethyl-1-oxo-2,3-dihydro-1H-inden-4-yl)methyl]butanoic Acid

To a solution of 87.0 g (301.7 mmol) of ethyl 2-[(2-ethyl-1-oxo-2,3-dihydro-1H-inden-4-yl)methyl]butanoate and 56.5 g (362.3 mmol, 1.2 eq.) of ethyl iodide in 100 ml of THF cooled to 0° C., a solution of 44.0 g (392.1 mmol, 1.3 eq.) of ^(t)BuOK in 400 ml of THF was added dropwise for 4 h, and the reaction mixture was then stirred overnight at room temperature. Further on, this mixture was evaporated on a Rotavapor. To the residue, a solution of 60 g of KOH in a mixture of 200 ml of water and 200 ml of methanol was added. The resulting mixture was refluxed for 4 h to saponificate the ester. Further on, methanol and water were distilled off until temperature reached 95° C., and 1.5 L of water and then 12 M HCl (to pH 1) were added to the residue. Crude product was extracted with 300 ml of dichloromethane. The aqueous phase was additionally extracted with 3×150 ml of dichloromethane. The combined organic extract was evaporated to dryness to give 84 g (ca. 100% yield) of 2-[(2,2-diethyl-1-oxo-2,3-dihydro-1H-inden-4-yl)methyl]butanoic acid as a red viscous oil which was further used without an additional purification.

¹H NMR (CDCl₃): δ 11.7 (br.s, 1H), 7.60 (d, J=7.6 Hz, 1H), 7.42 (d, J=7.3 Hz, 1H), 7.33-7.25 (m, 1H), 3.11-2.78 (m, 4H), 2.78-2.65 (m, 1H), 1.84-1.52 (m, 6H), 1.01 (t, J=7.3 Hz, 3H), 0.76 (t, J=7.6 Hz, 3H), 0.74 (t, J=7.6 Hz, 3H). ¹³C{¹H} NMR (CDCl₃): δ 211.80, 181.04, 152.16, 137.55, 136.70, 134.71, 127.61, 121.95, 53.40, 47.45, 35.47, 33.59, 29.86, 29.81, 25.22, 11.58, 8.59, 8.56.

2-[(2,2-Diethyl-2,3-dihydro-1H-inden-4-yl)methyl]butanoic Acid

To a solution of 2-[(2,2-diethyl-1-oxo-2,3-dihydro-1H-inden-4-yl)methyl]butanoic acid (as prepared above) in a mixture of 66 g (1.18 mol) of KOH and 540 ml of ethylene glycol, 53 ml of hydrazine hydrate was added. The reaction mixture was refluxed for 6 h. Then, 66 g of KOH and 26 ml of hydrazine hydrate were added, and the reaction mixture was additionally refluxed for 5 h. Further on, the reflux condenser was replaced by a Claisen distillation head with Liebig condenser, and a mixture of water, NH₂NH₂, and ethylene glycol was slowly distilled off until the distillation temperature reached 195° C. (ca. half of the initial volume). The residue was then allowed to cool to room temperature, diluted with 2 L of water, acidified with 12 N HCl to pH=1, and crude product was extracted with 3×300 ml of dichloromethane. The combined organic extract was washed with 1 L of water, and then evaporated to dryness to give 80.8 g [98% yield from ethyl 2-[(2-ethyl-1-oxo-2,3-dihydro-1H-inden-4-yl)methyl]butanoate] of the title product as a red viscous oil which was further used without an additional purification.

¹H NMR (CDCl₃): δ 11.8 (br.s, 1H), 7.08-6.98 (m, 2H), 6.93 (d, J=7.1 Hz, 1H), 2.92 (dd, J=13.4 Hz, J=7.3 Hz, 1H), 2.73 (s, 2H), 2.71-2.55 (m, 4H), 1.74-1.52 (m, 2H), 1.51-1.42 (m, 4H), 0.95 (t, J=7.3 Hz, 3H), 0.84 (t, J=7.3 Hz, 3H), 0.83 (t, J=7.3 Hz, 3H). ¹³C{¹H} NMR (CDCl₃): δ 182.34, 143.54, 142.03, 134.94, 126.48, 126.27, 122.70, 47.70, 45.94, 43.93, 42.30, 35.18, 30.56, 24.82, 11.71, 9.00.

2,7,7-Triethyl-1,6,7,8-tetrahydro-as-indacen-3(2H)-one

A mixture of the above-obtained 2-[(2,2-diethyl-2,3-dihydro-1H-inden-4-yl)methyl]butanoic acid (80.8 g, 295 mmol) and 150 ml (246 g, 2.07 mol) of thionyl chloride was stirred for 24 h at room temperature. An excess of thionyl chloride was distilled off, and the residue was dried in vacuum. The obtained 2-[(2,2-Diethyl-2,3-dihydro-1H-inden-4-yl)methyl]butanoyl chloride was further used without an additional purification. To a suspension of 47.2 g (354 mmol, 1.2 eq.) of AlCl₃ in 300 ml of dichloromethane cooled to 0° C., a solution of 2-[(2,2-diethyl-2,3-dihydro-1H-inden-4-yl)methyl]butanoyl chloride in 150 ml of dichloromethane was added over 1 h. The cooling bath was then removed, and the solution was stirred overnight at room temperature. The reaction mixture was poured into 500 g of crushed ice, the organic phase was separated, and the aqueous phase was extracted by 200 ml of dichloromethane. The combined organic extract was washed with aqueous K₂CO₃, dried over K₂CO₃, passed through a short pad of silica gel 60 (40-63 um), and the elute was evaporated to dryness to give 73.7 g (98% yield) of 2,7,7-triethyl-1,6,7,8-tetrahydro-as-indacen-3(2H)-one as a red oil which was further used without an additional purification.

¹H NMR (CDCl₃): δ 7.55 (d, J=7.6 Hz, 1H), 7.16 (d, J=7.6 Hz, 1H), 3.16 (dd, J=17.2 Hz, J=7.6 Hz, 1H), 2.80 (s, 2H), 2.71 (s, 2H), 2.69-2.55 (m, 2H), 2.06-1.91 (m, 1H), 1.59-1.43 (m, 5H), 1.01 (t, J=7.3 Hz, 3H), 0.87 (t, J=7.3 Hz, 3H), 0.86 (t, J=7.3 Hz, 3H). ¹³C{¹H} NMR (CDCl₃): δ 208.70, 150.90, 150.05, 140.44, 135.43, 123.77, 122.06, 49.04, 46.68, 44.29, 41.03, 30.90, 30.78, 30.71, 24.58, 11.66, 8.98, 8.94.

2,2,7-Triethyl-1,2,3,6-tetrahydro-as-indacene (Illustrated as the 2,2,7-Triethyl-1,2,3,8-tetrahydro-as-indacene Isomer)

To a solution of 73.7 g (288 mmol) of 2,7,7-triethyl-1,6,7,8-tetrahydro-as-indacen-3(2H)-one in 300 ml of THF cooled to 5° C., 16.3 g (431 mmol) of NaBH₄ was added. Further on, 150 ml of methanol was added dropwise to this vigorously stirred mixture for ca. 5 h at 5° C. The resulting mixture was stirred for 3 h at room temperature, then evaporated to dryness, and the residue was partitioned between 500 ml of dichloromethane and 500 ml of 2 M HCl. The organic layer was separated, and the aqueous layer was additionally extracted with 100 ml of dichloromethane. The combined organic extract was evaporated to dryness. To a solution of the residue in 500 ml of toluene, 1 g of TsOH was added, and this mixture was refluxed with a Dean-Stark head for 20 min., then cooled to room temperature using a water bath. The resulting solution was washed by 10% Na₂CO₃. The organic layer was separated, and the aqueous layer was extracted with 2×100 ml of dichloromethane. The combined organic extract was dried over K₂CO₃ and then passed through a short pad of silica gel 60 (40-63 um). The silica gel pad was additionally washed by 100 ml of dichloromethane. The combined organic elute was evaporated to dryness. This crude product was rectificated in vacuum to give 51.3 g (74% yield) of 2,2,7-triethyl-1,2,3,6-tetrahydro-as-indacene as a yellowish oil, b.p. 134° C.-137° C./5 mm Hg.

Anal. calc. for C₁₈H₂₄: C, 89.94; H, 10.06. Found: C, 90.23; H, 10.36.

¹H NMR (CDCl₃): δ 7.05 (d, J=7.6 Hz, 1H), 7.01 (d, J=7.6 Hz, 1H), 6.47 (s, 1H), 3.16 (s, 2H), 2.75 (s, 2H), 2.67 (s, 2H), 2.49 (q, J=7.3 Hz, 2H), 1.49 (q, J=7.3 Hz, 4H), 1.20 (q, J=7.3 Hz, 3H), 0.84 (q, J=7.3 Hz, 6H). ¹³C{¹H} NMR (CDCl₃): δ 150.82, 143.83, 139.24, 138.63, 138.08, 125.36, 122.27, 117.81, 46.63, 43.76, 41.96, 39.41, 30.68, 24.36, 13.43, 9.05.

Pre-Catalyst Synthesis:

Example 3: Synthesis of rac-dimethylsilanediyl-bis[η⁵-2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl]zirconium Dichloride (Pre-Catalyst A) Bis(2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(dimethyl)silane

To a solution of 19.8 g (100 mmol) of 2,2,7-trimethyl-1,2,3,8-tetrahydro-as-indacene in a mixture of 200 ml of toluene and 10 ml of THF, 40.0 ml (100.0 mmol) of 2.5 M ^(n)BuLi in hexanes was added in one portion at room temperature. This mixture was refluxed for 1 h, then the resulting light yellow solution with a large amount of white precipitate was cooled to 0° C., and 6.45 g (50.0 mmol) of dichlorodimethylsilane was added in one portion. Further on, this mixture was stirred overnight at ambient temperature. Then, the obtained mixture was quenched with 20 ml of water, the organic layer was separated, and the aqueous layer was extracted with 2×60 ml of toluene. The combined organic extract was filtered through a pad of silica gel 60 (40-63 um) which was additionally washed by 2×10 ml of toluene. The combined filtrate was evaporated under a reduced pressure to give a white solid mass. The latter was triturated with 750 ml of n-hexane, the precipitate was filtered through a glass frit (G4) and then dried in vacuo. This procedure gave 16.6 g (73% yield) of bis(2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(dimethyl)silane as a white powder (approx. 3:2 mixture of two stereoisomers).

Anal. calc. for C₃₂H₄₀Si: C, 84.89; H, 8.91. Found: C, 85.27; H, 9.30.

¹H NMR (CDCl₃): δ 7.30 (d, J=7.6 Hz), 7.15 (d, J=7.6 Hz), 6.95-6.85 (m), 6.53 (s), 3.70 (s), 3.68 (s), 2.85-2.69 (m), 2.23 (s), 2.17 (s), 1.20 (s), 1.19 (s), 1.17 (s), 1.16 (s), −0.31 (s), −0.33 (s). ¹³C{¹H} NMR (CDCl₃): δ 147.44, 147.31, 142.79, 142.73, 141.60, 141.53, 140.45, 134.48, 124.95, 124.87, 120.94, 119.07, 119.00, 47.80, 47.09, 47.01, 46.05, 40.40, 29.08, 18.00, −5.87, −5.96, −6.16.

Rac-dimethylsilanediyl-bis[η⁵-2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl]zirconium Dichloride (Pre-Catalyst A)

To a suspension of 4.53 g (10.0 mmol) of bis(2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(dimethyl)silane in 200 ml of ether cooled to −50° C., 8.0 ml (20.0 mmol) of 2.5 M ^(n)BuLi in hexanes was added in one portion. This mixture was stirred overnight at room temperature, then the resulting yellow suspension was cooled to −50° C., and 3.78 g (10.02 mmol) of ZrCl₄(THF)₂ was added. The reaction mixture was stirred for 24 h at room temperature to give orange suspension. This mixture was evaporated to dryness. The residue was heated with 200 ml of toluene, and the formed suspension was filtered while hot through a glass frit (G4). The filtrate was evaporated to 80 ml and then heated to dissolve the precipitate. Orange crystals precipitated from this solution within 2 h at room temperature and were collected, washed with 10 ml of n-hexane, and dried in vacuum. This procedure gave 1.98 g of pure rac-zirconocene. The mother liquor was evaporated to ca. 15 ml. Orange crystals precipitated from this solution overnight at room temperature and were collected and then dried in vacuum. This procedure gave 0.26 g of rac-zirconocene. Thus, the total yield of rac-dimethylsilanediyl-bis[η⁵-2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl]zirconium dichloride isolated in this synthesis was 2.24 g (36% yield).

Anal. calc. for C₃₂H₃₈Cl₂SiZr: C, 62.71; H, 6.25. Found: C, 62.95; H, 6.33.

¹H NMR (CD₂Cl₂): δ 7.50 (d, J=8.85 Hz, 2H), 6.92 (d, J=8.85 Hz, 2H), 6.55 (s, 2H), 2.94 (d, J=15.9 Hz, 2H), 2.78 (d, J=15.9 Hz, 2H), 2.72 (s, 4H), 2.20 (s, 6H), 1.28 (s, 6H), 1.27 (s, 6H), 1.15 (s, 6H). ¹H NMR (CDCl₃): δ 7.48 (d, J=8.7 Hz, 2H), 6.92 (d, J=8.7 Hz, 2H), 6.58 (s, 2H), 2.98 (d, J=16.1 Hz, 2H), 2.82 (d, J=16.5 Hz, 2H), 2.77 (d, J=16.5 Hz, 2H), 2.70 (d, J=16.1 Hz, 2H), 2.22 (s, 6H), 1.28 (s, 12H), 1.16 (s, 6H). ¹³C{¹H} NMR (CDCl₃): δ 141.42, 138.46, 135.13, 131.13, 126.53, 123.84, 123.34, 119.53, 83.42, 48.62, 46.96, 39.64, 29.93, 29.78, 18.60, 2.59.

Example 4: Synthesis of rac-dimethylsilanediyl-bis[η⁵-2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl]zirconium Dimethyl (Pre-Catalyst B) Rac-dimethylsilanediyl-bis[η⁵-2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl]zirconium Dimethyl (Pre-Catalyst B)

To a suspension of 919 mg (1.5 mmol) of rac-dimethylsilanediyl-bis[η⁵-2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl]zirconium dichloride in a mixture of 25 ml of toluene and 5 ml of ether, 3.0 ml (6.33 mmol) of 2.11 M MeMgBr in ether was added. The resulting heterogeneous mixture was stirred overnight at room temperature and, then, additionally refluxed for 10 min. The reaction mixture was evaporated to ca. 25 ml, heated and filtered while hot through a glass frit (G3) to remove insoluble magnesium salts. The filtrate was evaporated to ca. 20 ml, heated and again filtered while hot through a glass frit (G3). Yellow crystalline material precipitated from the obtained filtrate overnight at room temperature and was collected, washed with 5 ml of n-hexane, and dried in vacuum. This procedure gave 0.60 g of the title complex. The mother liquor was evaporated to ca. 3 ml. Yellow solid precipitated from this solution overnight at room temperature was filtered off and dried in vacuum. This procedure gave 0.15 g of the same complex. Thus, total yield of the title rac-complex isolated in this synthesis was 0.75 g (87% yield).

Anal. calc. for C₃₄H₄₄SiZr: C, 71.39; H, 7.75. Found: C, 71.19; H, 7.64.

¹H NMR (CDCl₃): δ 7.28 (d, J=8.84 Hz, 2H), 6.75 (d, J=8.84 Hz, 2H), 6.49 (s, 2H), 2.84 (d, J=15.9 Hz, 2H), 2.76 (d, J=16.2 Hz, 2H), 2.70 (d, J=16.2 Hz, 2H), 2.65 (d, J=15.9 Hz, 2H), 2.00 (s, 6H), 1.18 (s, 6H), 1.11 (s, 6H), 0.99 (s, 6H), −1.42 (s, 6H). ¹³C{¹H} NMR (CDCl₃): δ 138.25, 137.47, 134.28, 127.19, 127.00, 123.48, 121.68, 113.24, 79.19, 48.51, 47.35, 39.63, 34.78, 29.98, 18.10, 2.70.

Example 5: Synthesis of rac-dimethylsilanediyl-bis[η⁵-2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl]hafnium Dichloride (Pre-Catalyst C) Rac-dimethylsilanediyl-bis[η⁵-2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl]hafnium Dichloride (Pre-Catalyst C)

To a suspension of 11.9 g (26.3 mmol) of bis(2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(dimethyl)silane in 450 ml of ether cooled to −78° C., 21.1 ml (52.75 mmol) of 2.5 M ^(n)BuLi in hexanes was added in one portion. This mixture was stirred overnight at room temperature, then the resulting light orange suspension was cooled to −50° C., and 12.2 g (26.3 mmol) of HfCl₄(THF)₂ was added. The reaction mixture was stirred for 24 h at room temperature and then evaporated to dryness. The residue was heated with 300 ml of toluene, and the formed suspension was filtered while hot through a glass frit (G4). The filtrate was evaporated to 150 ml and heated to dissolve the precipitate. Yellow crystals precipitated from this solution overnight at room temperature and were collected and dried in vacuum. This procedure gave 5.95 g of pure rac-hafnocene. The mother liquor was evaporated to ca. 40 ml. Yellow crystals precipitated from this solution overnight at −30° C. and were collected and then dried in vacuum. This procedure gave 0.63 g of rac-hafnocene. Thus, the total yield of rac-dimethylsilanediyl-bis[η⁵-2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl]hafnium dichloride isolated in this synthesis was 6.58 g (36% yield).

Anal. calc. for C₃₂H₃₈Cl₂SiZr: C, 62.71; H, 6.25. Found: C, 62.92; H, 6.49.

¹H NMR (CDCl₃): δ 7.51 (d, J=8.84 Hz, 2H), 6.88 (d, J=8.84 Hz, 2H), 6.47 (s, 2H), 3.01 (d, J=15.9 Hz, 2H), 2.81 (d, J=15.9 Hz, 2H), 2.78 (d, J=16.2 Hz, 2H), 2.68 (d, J=16.2 Hz, 2H), 2.30 (s, 6H), 1.26 (s, 6H), 1.25 (s, 6H), 1.15 (s, 6H). ¹³C{¹H} NMR (CDCl₃): δ 141.20, 138.03, 132.51, 130.71, 124.90, 123.54, 123.34, 117.64, 84.50, 48.59, 46.99, 39.63, 29.93, 29.81, 18.45, 2.57.

Example 6: Synthesis of rac-dimethylsilanediyl-bis[η⁵-2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl] hafnium Dimethyl (Pre-Catalyst D) Rac-dimethylsilanediyl-bis[η⁵-2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl] hafnium Dimethyl (Pre-Catalyst D)

To a suspension of 1.40 g (2.0 mmol) of rac-dimethylsilanediyl-bis[η⁵-2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl]hafnium dichloride in 40 ml of toluene, 3.80 ml (8.02 mmol) of 2.11 M MeMgBr in ether was added. The resulting heterogeneous mixture was stirred overnight at room temperature and then additionally refluxed for 10 min. The reaction mixture was evaporated to ca. 25 ml, heated and filtered while hot through a glass frit (G3) to remove insoluble magnesium salts. The filtrate was evaporated to ca. 20 ml, heated and again filtered while hot through a glass frit (G4). Yellow crystalline material precipitated from the obtained filtrate overnight at −30° C. and was collected, washed with 5 ml of n-hexane, and dried in vacuum. This procedure gave 1.06 g (80% yield) of pure target complex.

Anal. calc. for C₃₄H₄₄HfSi: C, 61.94; H, 6.73. Found: C, 61.80; H, 6.91.

¹H NMR (CDCl₃): δ 7.4 (d, J=8.84 Hz, 2H), 6.82 (d, J=8.84 Hz, 2H), 6.47 (s, 2H), 2.94 (d, J=16.0 Hz, 2H), 2.82 (d, J=11.6 Hz, 2H), 2.78 (d, J=11.6 Hz, 2H), 2.71 (d, J=16.0 Hz, 2H), 2.12 (s, 6H), 1.25 (s, 6H), 1.18 (s, 6H), 1.08 (s, 6H), −1.54 (s, 6H). ¹³C{¹H} NMR (CDCl₃): δ 138.31, 137.18, 132.75, 127.19, 126.36, 123.45, 121.73, 112.26, 81.28, 48.54, 47.41, 40.38, 39.61, 30.00 (two resonances), 17.94, 2.66.

Example 7: Synthesis of 1,1-silolanediyl-bis(η⁵-2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)hafnium Dichloride (Pre-Catalyst E) 1,1-Bis(2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)silolane

To a solution of 14.9 g (75.0 mmol) of 2,2,7-trimethyl-1,2,3,8-tetrahydro-as-indacene in 250 ml of ether, 30.0 ml (75.0 mmol) of 2.5 M ^(n)BuLi in hexanes was added in one portion at −50° C. This mixture was stirred overnight at room temperature. Then, the obtained white suspension was cooled to −40° C., and 1.0 g (11.2 mmol) of CuCN was added. The resulting mixture was stirred for 30 min. at −25° C., and then 5.82 g (37.53 mmol) of 1,1-dichlorosilolane was added in one portion. This mixture was stirred for 3 h at ambient temperature, then filtered through a pad of silica gel 60 (40-63 um) which was additionally washed by 2×50 ml of dichloromethane. The combined filtrate was evaporated under reduced pressure, and the product was isolated by flash-chromatography using 200 ml of silica gel 60 (40-63 um; eluent: hexanes-dichloromethane=10:1, vol.). This procedure gave 15.25 g (85% yield) of 1,1-bis(2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)silolane (approx. 3:2 mixture of two isomers) as a slightly yellowish glass.

Anal. calc. for C₃₄H₄₂Si: C, 85.29; H, 8.84. Found: C, 85.53; H, 9.10.

¹H NMR (CDCl₃): δ 7.14 (d, J=7.3 Hz), 6.97 (d, J=7.3 Hz), 6.88 (d, J=7.3 Hz), 6.84 (d, J=7.3 Hz), 6.48 (s), 6.36 (s), 3.31 (s), 2.88-2.55 (m), 2.10 (s), 2.00 (s), 0.93-0.32 (m).

1,1-Silolanediyl-bis(η⁵-2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)hafnium Dichloride (Pre-Catalyst E)

To a solution of 15.25 g (31.9 mmol) of 1,1-bis(2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)silolane in 400 ml of ether cooled to −50° C., 25.5 ml (63.8 mmol) of 2.5 M ^(n)BuLi in hexanes was added in one portion. This mixture was stirred overnight at room temperature, then the resulting red solution was cooled to −50° C., and 14.8 g (31.9 mmol) of HfCl₄(THF)₂ was added. The reaction mixture was stirred for 24 h at room temperature to give orange suspension. This mixture was evaporated to dryness. The residue was heated with 200 ml of toluene, and the formed suspension was filtered while hot through a glass frit (G4). The filtrate was evaporated to ca. 80 ml. Yellow crystals precipitated from this solution overnight at −30° C. and were collected, washed with 15 ml of cold n-hexane, and dried in vacuum. This procedure gave 5.30 g (23%) of pure rac-1,1-silolanediyl-bis(η⁵-2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)hafnium dichloride. The mother liquor was evaporated to ca. 40 ml, and to this solution 20 ml of n-hexane was added. Yellow crystalline material precipitated from this solution overnight at −30° C. was collected and dried in vacuum. This procedure gave 4.20 g (18% yield) of a ca. 60 to 40 mixture of rac- and meso-hafnocenes. Thus, the total yield of rac- and meso-1,1-silolanediyl-bis(η⁵-2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)hafnium dichloride isolated in this synthesis was 9.50 g (41% yield).

Anal. calc. for C₃₄H₄₀Cl₂HfSi: C, 56.24; H, 5.55. Found: C, 56.21; H, 5.68.

¹H NMR (CDCl₃): δ 7.44 (d, J=8.8 Hz), 6.88 (d, J=8.8 Hz), 6.46 (s), 3.02 (d, J=16.2 Hz), 2.84 (s), 2.80 (s), 2.76 (s), 2.68 (d, J=16.2 Hz), 2.29 (s), 2.18-2.06 (m), 2.01-1.91 (m), 1.91-1.81 (m), 1.27 (s), 1.15 (s). ¹³C{¹H} NMR (CDCl₃): δ 141.34, 138.02, 132.44, 130.89, 124.08, 123.28, 123.20, 116.43, 84.15, 48.59, 46.98, 39.63, 29.91, 29.77, 26.86, 18.20, 14.59.

Example 8: Synthesis of tetramethyldisilanediyl-bis[η⁵-2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl]zirconium Dichloride (Pre-Catalyst F (rac) and G (meso)) 1,1,2,2-Tetramethyl-1,2-bis(2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)disilane

To a solution of 14.9 g (75.0 mmol) of 2,2,7-trimethyl-1,2,3,8-tetrahydro-as-indacene in 250 ml of ether, 30.0 ml (75.0 mmol) of 2.5 M ^(n)BuLi in hexanes was added in one portion at −50° C. This mixture was stirred overnight at room temperature. Then, the resulting white suspension was cooled to −40° C., and 1.0 g (11.2 mmol) of CuCN was added. The obtained mixture was stirred for 30 min. at −25° C., and then 7.02 g (37.5 mmol) of 1,2-dichloro-1,1,2,2-tetramethyldisilane was added in one portion. This mixture was stirred for 3 h at ambient temperature, then filtered through a pad of silica gel 60 (40-63 um) which was additionally washed by 2×50 ml of dichloromethane. The combined filtrate was evaporated under reduced pressure, and the residue was dissolved in 60 ml of n-hexane. White solid precipitated overnight at −30° C. was collected and dried in vacuum. This procedure gave 10.27 g of 1,1,2,2-tetramethyl-1,2-bis(2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)disilane. Additional amount of the product was isolated by flash-chromatography (from the residue after evaporation of the mother liquor) using 350 ml of silica gel 60 (40-63 um; eluent: hexanes-dichloromethane=10:1, vol.). This procedure gave extra 4.25 g of the title product. Thus, the total yield of 1,1,2,2-tetramethyl-1,2-bis(2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)disilane isolated in this synthesis was 14.52 g (76% yield).

Anal. calc. for C₃₄H₄₆Si₂: C, 79.93; H, 9.08. Found: C, 80.23; H, 9.37.

Major Isomer:

¹H NMR (CDCl₃): δ 7.04 (d, J=7.6 Hz, 2H), 6.86 (d, J=7.6 Hz, 2H), 6.36 (s, 2H), 3.09 (s, 2H), 2.81-2.67 (m, 8H), 2.02 (s, 6H), 1.18 (s, 6H), 1.13 (s, 6H), 0.1 (s, 6H), −0.35 (s, 6H). ¹³C{¹H} NMR (CDCl₃): δ 148.42, 143.48, 140.94, 140.20, 134.25, 123.82, 120.78, 118.82, 49.23, 47.79, 46.03, 40.41, 29.01, 29.00, 17.85, −1.05, −2.01.

Minor Isomer:

¹H NMR (CDCl₃): δ 6.95 (d, J=7.6 Hz, 2H), 6.82 (d, J=7.6 Hz, 2H), 6.42 (s, 2H), 3.14 (s, 2H), 2.81-2.67 (m, 8H), 2.11 (s, 6H), 1.18 (s, 6H), 1.14 (s, 6H), −0.04 (s, 6H), −0.28 (s, 6H). ¹³C{¹H} NMR (CDCl₃): δ 148.37, 143.41, 140.84, 140.24, 134.19, 123.90, 120.84, 118.87, 49.17, 47.79, 46.05, 40.43, 29.02, 29.00, 17.97, −1.22, −2.05.

Tetramethyldisilanediyl-bis[η⁵-2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl]zirconium Dichloride (Pre-Catalyst F (rac) and G (meso))

To a solution of 5.11 g (10.0 mmol) of 1,1,2,2-tetramethyl-1,2-bis(2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)disilane in 150 ml of ether cooled to −78° C., 8.0 ml (20.0 mmol) of 2.5 M ^(n)BuLi in hexanes was added in one portion. This mixture was stirred overnight at room temperature, then the resulting yellowish suspension was cooled to −30° C., and 3.77 g (10.0 mmol) of ZrCl₄(THF)₂ was added. The reaction mixture was stirred for 24 h at room temperature to give orange suspension. This mixture was evaporated to dryness. The residue was heated with 200 ml of toluene, and the formed suspension was filtered while hot through a glass frit (G4) to give a filtrate including on the evidence of NMR spectroscopy a ca. 2 to 1 mixture of rac- and meso-zirconocenes. Pure isomeric complexes were obtained using multiple crystallizations of this mixture from toluene-n-octane. This procedure gave 1.50 g (22% yield) and 0.57 g (9% yield) of rac- and meso-complexes, respectively.

Rac-zirconocene

Anal. calc. for C₃₄H₄₄Cl₂Si₂Zr: C, 60.86; H, 6.61. Found: C, 60.75; H, 6.82.

¹H NMR (CDCl₃): δ 7.47 (d, J=8.6 Hz, 2H), 7.02 (d, J=8.6 Hz, 2H), 6.33 (s, 2H), 2.99 (d, J=15.9 Hz, 2H), 2.92 (d, J=16.4 Hz, 2H), 2.78 (d, J=15.9 Hz, 2H), 2.67 (d, J=16.4 Hz, 2H), 2.04 (s, 6H), 1.28 (s, 6H), 1.13 (s, 6H), 0.85 (s, 6H), 0.54 (s, 6H). ¹³C{¹H} NMR (CDCl₃): δ 140.79, 138.88, 138.63, 133.55, 125.74, 123.12, 122.03, 116.69, 108.14, 48.64, 47.29, 39.52, 30.12, 29.81, 18.28, −0.05, −0.33.

Meso-Zirconocene

Anal. calc. for C₃₄H₄₄Cl₂Si₂Zr: C, 60.86; H, 6.61. Found: C, 61.09; H, 6.78.

¹H NMR (CDCl₃): δ 7.45 (d, J=8.6 Hz, 2H), 6.82 (d, J=8.6 Hz, 2H), 6.29 (s, 2H), 2.96 (d, J=16.2 Hz, 2H), 2.61 (s, 4H), 2.58 (d, J=16.2 Hz, 2H), 2.42 (s, 6H), 1.07 (s, 6H), 1.05 (s, 6H), 0.74 (s, 6H), 0.62 (s, 6H). ¹³C{¹H} NMR (CDCl₃): δ 144.36, 139.46, 137.87, 132.76, 128.51, 123.66, 121.71, 113.09, 108.19, 48.52, 47.17, 39.63, 29.68, 29.62, 20.12, 0.46, −0.48.

Example 9: Synthesis of tetramethyldisilanediyl-bis[η⁵-2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl]hafnium Dichloride (Pre-Catalyst H (rac) and I (meso)) Tetramethyldisilanediyl-bis[η⁵-2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl]hafnium Dichloride (Pre-Catalyst H (rac) and I (meso))

To a solution of 9.33 g (18.3 mmol) of 1,1,2,2-tetramethyl-1,2-bis(2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)disilane in 250 ml of ether cooled to −78° C., 14.6 ml (36.5 mmol) of 2.5 M ^(n)BuLi in hexanes was added in one portion. This mixture was stirred overnight at room temperature, then the resulting slightly yellowish suspension was cooled to −30° C., and 8.48 g (18.0 mmol) of HfCl₄(THF)₂ was added. The reaction mixture was stirred for 24 h at room temperature to give orange suspension. This mixture was evaporated to dryness. The residue was heated with 200 ml of toluene, and the formed suspension was filtered while hot through a glass frit (G4). The filtrate was evaporated to 30 ml and heated to dissolve the precipitate. Yellowish crystals precipitated from this solution over 3 days at room temperature were collected and dried in vacuum. This procedure gave 2.60 g (19% yield) of pure rac-hafnocene. The mother liquor was evaporated to dryness, and the residue was dissolved in 70 ml of hot n-octane. Solid precipitated from this solution overnight at room temperature was filtered and discarded. Yellow crystals precipitated from the filtrate overnight at −30° C. were collected and dried in vacuum. This procedure gave 0.7 g (5% yield) of pure meso-hafnocene.

Rac-Hafnocene.

Anal. calc. for C₃₄H₄₄Cl₂HfSi₂: C, 53.85; H, 5.85. Found: C, 54.16; H, 6.03.

¹H NMR (CDCl₃): δ 7.46 (d, J=8.6 Hz, 2H), 6.98 (d, J=8.6 Hz, 2H), 6.21 (s, 2H), 3.03 (d, J=15.8 Hz, 2H), 2.88 (d, J=16.2 Hz, 2H), 2.83 (d, J=15.8 Hz, 2H), 2.67 (d, J=16.2 Hz, 2H), 2.11 (s, 6H), 1.27 (s, 6H), 1.14 (s, 6H), 0.84 (s, 6H), 0.54 (s, 6H). ¹³C{¹H} NMR (CDCl₃): δ 140.60, 138.47, 137.08, 133.23, 124.40, 122.78, 122.27, 114.61, 105.86, 48.58, 47.30, 39.52, 30.09, 29.83, 18.11, 0.02, −0.33.

Meso-Hafnocene.

Anal. calc. for C₃₄H₄₄Cl₂HfSi₂: C, 53.85; H, 5.85. Found: C, 54.87; H, 5.98.

¹H NMR (CDCl₃): δ 7.46 (d, J=8.6 Hz, 2H), 6.78 (d, J=8.6 Hz, 2H), 6.17 (s, 2H), 2.93 (d, J=16.4 Hz, 2H), 2.72-2.62 (m, 4H), 2.58 (d, J=16.4 Hz, 2H), 2.51 (s, 6H), 1.08 (s, 6H), 1.04 (s, 6H), 0.74 (s, 6H), 0.61 (s, 6H). ¹³C{¹H} NMR (CDCl₃): δ 143.80, 139.24, 137.53, 132.30, 127.26, 124.00, 121.43, 110.64, 104.92, 48.47, 47.23, 39.61, 29.65, 29.63, 20.02, 0.51, −0.47.

Example 10: Synthesis of rac-tetramethyldisilanediyl-bis[η⁵-2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl]hafnium Dimethyl (Pre-Catalyst J) Rac-tetramethyldisilanediyl-bis[η⁵-2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl]hafnium Dimethyl (Pre-Catalyst J)

To a solution of 1.14 g (1.5 mmol) of rac-tetramethyldisilanediyl-bis[η⁵-2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl]hafnium dichloride in 30 ml of toluene, 3.0 ml (6.33 mmol) of 2.11 M MeMgBr in ether was added. The resulting mixture was stirred overnight at room temperature and then additionally refluxed for 10 min. The reaction mixture was evaporated to ca. 20 ml, heated, and filtered while hot through a glass frit (G3) to remove insoluble magnesium salts. The filtrate was evaporated to dryness, 20 ml of n-hexane was added, and the resulting mixture was heated again and filtered while hot through a glass frit (G4). The filtrate was evaporated to ca. 10 ml and heated to dissolve the precipitate. Crystalline material precipitated from this solution overnight at room temperature was collected and dried in vacuum. This procedure gave 0.58 g (54% yield) of the target complex.

Anal. calc. for C₃₆H₅₀HfSi₂: C, 60.27; H, 7.02. Found: C, 60.12; H, 7.35.

¹H NMR (CDCl₃): δ 7.32 (d, J=8.6 Hz, 2H), 6.91 (d, J=8.6 Hz, 2H), 6.32 (s, 2H), 3.00-2.71 (m, 8H), 2.07 (s, 6H), 1.25 (s, 6H), 1.19 (s, 6H), 0.64 (s, 6H), 0.63 (s, 6H), −1.48 (s, 6H). ¹³C{¹H} NMR (CDCl₃): δ 137.83, 137.27, 133.56, 128.10, 126.63, 122.64, 121.44, 110.68, 100.42, 48.52, 47.65, 41.38, 39.59, 29.99, 17.64, 0.03.

Example 11: Synthesis of rac-dimethylsilanediyl-bis[η⁵-2,7,7-triethyl-3,6,7,8-tetrahydro-as-indacen-3-yl]zirconium Dichloride (Pre-Catalyst K) dimethylbis(2,7,7-triethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)silane

To a solution of 16.0 g (66.6 mmol) of 2,2,7-triethyl-1,2,3,8-tetrahydro-as-indacene in a mixture of 250 ml of toluene and 12.5 ml of THF, 26.6 ml (66.5 mmol) of 2.5 M ^(n)BuLi in hexanes was added in one portion at room temperature. This mixture was refluxed for 2 h, then the resulting light yellow solution was cooled to room temperature, and 4.30 g (33.3 mmol) of dichlorodimethylsilane was added in one portion. Further on, this mixture was refluxed for 3 h and then cooled to room temperature. This mixture was quenched with 1 ml of water, filtered through a pad of silica gel 60 (40-63 um) which was additionally washed by 3×50 ml of dichloromethane. The combined filtrate was evaporated under reduced pressure to give a yellowish oil. The product was isolated by flash-chromatography using 200 ml of silica gel 60 (40-63 um; eluent: hexane-dichloromethane=10:1, vol.). This procedure gave 15.6 g (87% yield) of 1,1-bis(2,7,7-triethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)silolane (approx. 4:3 mixture of isomers) as a yellowish oil.

Anal. calc. for C₃₈H₅₂Si: C, 85.01; H, 9.76. Found: C, 85.47; H, 9.94.

¹H NMR (CDCl₃): δ 7.33 (d, J=7.6 Hz), 7.16 (d, J=7.6 Hz), 6.96-6.87 (m), 6.63-6.57 (m), 3.79 (s), 3.74 (s), 2.91-2.73 (m), 2.73-2.36 (m), 1.63-1.47 (m), 1.35-1.18 (m), 0.96-0.83 (m), −0.29 (s), −0.33 (s), −0.34 (s).

rac-Dimethylsilanediyl-bis[η⁵-2,7,7-triethyl-3,6,7,8-tetrahydro-as-indacen-3-yl]zirconium Dichloride (Pre-Catalyst K)

To a solution of 15.6 g (29.06 mmol) of bis(2,7,7-triethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(dimethyl)silane in 300 ml of ether cooled to −50° C., 23.3 ml (58.3 mmol) of 2.5 M ^(n)BuLi in hexanes was added in one portion. This mixture was stirred overnight at room temperature, then the resulting yellow suspension was cooled to −50° C., and 11.0 g (29.1 mmol) of ZrCl₄(THF)₂ was added. The reaction mixture was stirred for 24 h at room temperature to give bright orange suspension. This mixture was evaporated to dryness. The residue was heated with 200 ml of toluene, and the formed suspension was filtered while hot through a glass frit (G4). The filtrate was evaporated to 80 ml, and 20 ml of n-octane was added to this warm solution. Orange crystals precipitated from the formed solution overnight at room temperature and were collected and dried in vacuum. This procedure gave 4.40 g of pure rac-zirconocene. The mother liquor was evaporated to ca. 60 ml, heated almost to reflux, and 40 ml of n-octane was added. Orange powder precipitated from this solution overnight at room temperature was collected and dried in vacuum. This procedure gave 1.45 g of rac-zirconocene. Thus, the total yield of rac-dimethylsilanediyl-bis[η⁵-2,7,7-triethyl-3,6,7,8-tetrahydro-as-indacen-3-yl]zirconium dichloride isolated in this synthesis was 5.85 g (29% yield).

Anal. calc. for C₃₈H₅₀Cl₂SiZr: C, 65.48; H, 7.23. Found: C, 65.63; H, 7.20.

¹H NMR (CDCl₃): δ 7.45 (d, J=8.8 Hz, 2H), 6.90 (d, J=8.8 Hz, 2H), 6.62 (s, 2H), 2.97 (d, J=16.3 Hz, 2H), 2.82-2.65 (m, 8H), 2.44-2.31 (m, 2H), 1.66-1.54 (m, 4H), 1.46 (q, J=7.3 Hz, 4H), 1.27 (s, 6H), 1.10 (t, J=7.3 Hz, 6H), 0.88 (t, J=7.3 Hz, 6H), 0.80 (t, J=7.3 Hz, 6H). ¹³C{¹H} NMR (CDCl₃): δ 142.27, 141.12, 138.43, 131.14, 126.59, 123.78, 123.33, 117.06, 82.35, 46.04, 44.51, 43.17, 31.44, 31.09, 25.97, 16.96, 9.18, 8.83, 2.92.

Example 12: Synthesis of rac-1,1-silolanediyl-bis(η⁵-2,7,7-triethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)hafnium Dichloride (Pre-Catalyst L) 1,1-Bis(2,7,7-triethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)silolane

To a solution of 18.1 g (75.3 mmol) of 2,2,7-triethyl-1,2,3,8-tetrahydro-as-indacene in 300 ml of ether, 30.1 ml (75.3 mmol) of 2.5 M ^(n)BuLi in hexanes was added in one portion at −50° C. This mixture was stirred overnight at room temperature. Then, the resulting yellowish precipitate was cooled to −60° C., and 1.69 g (18.9 mmol, 25 mol %) of CuCN was added. The resulting mixture was stirred for 30 min. at −25° C., and then 5.84 g (37.7 mmol) of 1,1-dichlorosilolane was added in one portion. This mixture was stirred overnight at ambient temperature, then filtered through a pad of silica gel 60 (40-63 um) which was additionally washed by 2×50 ml of dichloromethane. The combined filtrate was evaporated under reduced pressure, and the product was isolated by flash-chromatography on silica gel 60 (40-63 um; eluent: hexanes-dichloromethane=10:1, vol.). This procedure gave 17.64 g (83% yield) of 1,1-bis(2,7,7-triethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)silolane (approx. 3:2 mixture of isomers) as a slightly yellowish oil.

Anal. calc. for C₄₀H₅₄Si: C, 85.34; H, 9.67. Found: C, 85.69; H, 9.80.

¹H NMR (CDCl₃): δ 7.13 (d, J=7.6 Hz), 6.98 (d, J=7.6 Hz), 6.88 (d, J=7.6 Hz), 6.84 (d, J=7.6 Hz), 6.51 (s), 6.37 (s), 3.36 (s), 2.85-2.69 (m), 2.58-2.12 (m), 1.57-1.42 (m), 1.41-0.98 (m), 1.13 (t, J=7.4 Hz), 1.11 (t, J=7.4 Hz), 0.89-0.80 (m), 0.54 (t, J=7.2 Hz), 0.32 (t, J=7.2 Hz).

rac-1,1-Silolanediyl-bis(η⁵-2,7,7-triethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)hafnium Dichloride (Pre-Catalyst L)

To a solution of 17.6 g (31.3 mmol) of 1,1-bis(2,7,7-triethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)silolane in 300 ml of ether cooled to −50° C., 25.1 ml (62.8 mmol) of 2.5 M ^(n)BuLi in hexanes was added in one portion. This mixture was stirred overnight at room temperature, then the resulting orange solution was cooled to −50° C., and 10.04 g (31.35 mmol) of HfCl₄ was added. The reaction mixture was stirred for 24 h at room temperature to give orange-red solution. This mixture was evaporated to dryness. The residue was heated with 200 ml of toluene, and the formed suspension was filtered while hot through a glass frit (G4). The filtrate was evaporated to dryness, and the residue was dissolved in 50 ml of warm n-hexane. Yellow crystals precipitated from this solution for a week at room temperature and were collected and dried in vacuum. This procedure gave 5.14 g (20% yield) of pure rac-1,1-silolanediyl-bis(η⁵-2,7,7-triethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)hafnium dichloride.

Anal. calc. for C₄₀H₅₂Cl₂HfSi: C, 59.29; H, 6.47. Found: C, 59.51; H, 6.62.

¹H NMR (CDCl₃): δ 7.41 (d, J=8.8 Hz, 2H), 6.86 (d, J=8.8 Hz, 2H), 6.50 (s, 2H), 3.01 (d, J=16.3 Hz, 2H), 2.87-2.63 (m, 8H), 2.48-2.35 (m, 2H), 2.20-2.08 (m, 2H), 1.99-1.79 (m, 6H), 1.67-1.51 (m, 4H), 1.46 (q, J=7.4 Hz, 4H), 1.10 (t, J=7.4 Hz, 6H), 0.88 (t, J=7.4 Hz, 6H), 0.80 (t, J=7.4 Hz, 6H). ¹³C{¹H} NMR (CDCl₃): δ 141.01, 139.50, 138.03, 130.84, 124.10, 123.24, 123.19, 114.3.

Polymerization Examples

Solutions of the pre-catalysts were made using toluene (ExxonMobil Chemical anhydrous, stored under N2) (98%). Pre-catalyst solutions were typically 0.5 mmol/L.

Solvents, polymerization grade toluene and/or isohexanes were supplied by ExxonMobil Chemical Co. and are purified by passing through a series of columns: two 500 cc Oxyclear cylinders in series from Labclear (Oakland, Calif.), followed by two 500 cc columns in series packed with dried 3 Å mole sieves (8-12 mesh; Aldrich Chemical Company), and two 500 cc columns in series packed with dried 5 Å mole sieves (8-12 mesh; Aldrich Chemical Company).

1-octene (C8; 98%, Aldrich Chemical Company) was dried by stirring over NaK overnight followed by filtration through basic alumina (Aldrich Chemical Company, Brockman Basic 1).

Polymerization grade ethylene (C2) was used and further purified by passing it through a series of columns: 500 cc Oxyclear cylinder from Labclear (Oakland, Calif.) followed by a 500 cc column packed with dried 3 Å mole sieves (8-12 mesh; Aldrich Chemical Company), and a 500 cc column packed with dried 5 Å mole sieves (8-12 mesh; Aldrich Chemical Company).

Polymerization grade propylene (C3) was used and further purified by passing it through a series of columns: 2250 cc Oxiclear cylinder from Labclear followed by a 2250 cc column packed with 3 Å mole sieves (8-12 mesh; Aldrich Chemical Company), then two 500 cc columns in series packed with 5 Å mole sieves (8-12 mesh; Aldrich Chemical Company), then a 500 cc column packed with Selexsorb CD (BASF), and finally a 500 cc column packed with Selexsorb COS (BASF).

Activation of the pre-catalysts was either by methylalumoxane (MAO, 10 wt % in toluene, Albemarle Corp.; Act ID=1), dimethylanilinium tetrakisperfluorophenylborate (Boulder Scientific or Albemarle Corp; Act ID=2) or dimethylanilinium tetrakisperfluoronaphthylborate (Albemarle Corp; Act ID=3). MAO was used as a 0.5 wt % or 1.0 wt % in toluene solution. Micromoles of MAO reported in the experimental section are based on the micromoles of aluminum in MAO. The formula weight of MAO is 58.0 grams/mole. Dimethylanilinium tetrakisperfluorophenylborate and dimethylanilinium tetrakis(perfluoronaphthyl)borate were typically used as a 5 mmol/L solution in toluene.

For polymerization runs using dimethylanilinium tetrakisperfluorophenylborate or dimethylanilinium tetrakisperfluoronaphthylborate, tri-n-octylaluminum (TnOAl, Neat, AkzoNobel) was also used as a scavenger prior to introduction of the activator and pre-catalyst into the reactor. TnOAl was typically used as a 5 mmol/L solution in toluene.

Reactor Description and Preparation:

Polymerizations were conducted in an inert atmosphere (N2) drybox using autoclaves equipped with an external heater for temperature control, glass inserts (internal volume of reactor=23.5 mL for C2 and C2/C8; 22.5 mL for C3 and C2/C3 runs), septum inlets, regulated supply of nitrogen, ethylene and propylene, and equipped with disposable PEEK mechanical stirrers (800 RPM). The autoclaves were prepared by purging with dry nitrogen at 110° C. or 115° C. for 5 hours and then at 25° C. for 5 hours.

Ethylene Polymerization (PE) or Ethylene/1-Octene Copolymerization (EO):

The reactor was prepared as described above, and then purged with ethylene. For MAO (Act ID=1) activated runs, toluene, 1-octene (100 μL when used), and activator (MAO) were added via syringe at room temperature and atmospheric pressure. The reactor was then brought to process temperature (80° C.) and charged with ethylene to process pressure (75 psig=618.5 kPa or 200 psig=1480.3 kPa) while stirring at 800 RPM. The pre-catalyst solution was then added via syringe to the reactor at process conditions. For dimethylanilinium tetrakisperfluorophenylborate (Act ID=2) activated runs, toluene, 1-octene (100 μL when used) and scavenger (TnOA1, 0.5 μmol) were added via syringe at room temperature and atmospheric pressure. The reactor was then brought to process temperature (80° C.) and charged with ethylene to process pressure (75 psig=618.5 kPa or 200 psig=1480.3 kPa) while stirring at 800 RPM. The activator solution, followed by the pre-catalyst solution, was injected via syringe to the reactor at process conditions. Ethylene was allowed to enter (through the use of computer controlled solenoid valves) the autoclaves during polymerization to maintain reactor gauge pressure (+/−2 psig). Reactor temperature was monitored and typically maintained within +/−1° C. Polymerizations were halted by addition of approximately 50 psi O₂/Ar (5 mole % O₂) gas mixture to the autoclave for approximately 30 seconds. The polymerizations were quenched after a predetermined cumulative amount of ethylene had been added (maximum quench value in psid) or for a maximum of 30 minutes polymerization time. Afterwards, the reactors were cooled and vented. Polymers were isolated after the solvent was removed in-vacuo. Yields reported include total weight of polymer and residual catalyst. Catalyst activity is reported as grams of polymer per mmol transition metal compound per hour of reaction time (g/mmol·hr). Ethylene homopolymerization runs are summarized in Table 1, and ethylene/1-octene copolymerization runs are summarized in Table 2.

Propylene Polymerization (PP):

The reactor was prepared as described above, then heated to 40° C., and then purged with propylene gas at atmospheric pressure. For MAO activated runs, toluene or isohexane, MAO, and liquid propylene (1.0 mL) were added via syringe. The reactor was then heated to process temperature (70° C. or 100° C.) while stirring at 800 RPM. The pre-catalyst solution was added via syringe with the reactor at process conditions. For dimethylanilinium tetrakisperfluorophenylborate or dimethylanilinium tetrakisperfluoronaphthylborate activated runs, isohexanes, liquid propylene (1.0 mL) and scavenger (TnOA1, 0.5 μmol) were added via syringe. The reactor was then brought to process temperature (70 or 100° C.) while stirring at 800 RPM. The activator solution, followed by the pre-catalyst solution, were injected via syringe to the reactor at process conditions. Reactor temperature was monitored and typically maintained within +/−1° C. Polymerizations were halted by addition of approximately 50 psi O₂/Ar (5 mole % O₂) gas mixture to the autoclaves for approximately 30 seconds. The polymerizations were quenched based on a predetermined pressure loss (maximum quench value) or for a maximum of 30 min. The reactors were cooled and vented. The polymers were isolated after the solvent was removed in-vacuo. The actual quench time (s) is reported as quench time (s). Yields reported include total weight of polymer and residual catalyst. Catalyst activity is reported as grams of polymer per mmol transition metal compound per hour of reaction time (g/mmol·hr). Propylene homopolymerization examples are reported in Table 3 with additional characterization in Table 4.

Propylene Polymerization and Ethylene-Propylene Copolymerization (EP):

The reactor was prepared as described above, then heated to 40° C. and then purged with ethylene gas at atmospheric pressure for reactors using ethylene. The listed ethylene pressure (10, 20, 40, 60, or 80 psid) was then added to the reactor. Isohexanes and scavenger (TnOA1, 0.5 μmol) were added via syringe. The stirrers were then started and maintained at 800 RPM. Liquid propylene (1.0 ml) was then injected into the reactor. The reactor was then brought to process temperature (70° C.). The activator solution, followed by the pre-catalyst solution, was injected via syringe to the reactor at process conditions. Reactor temperature was monitored and typically maintained within +/−1° C. Polymerizations were halted by addition of approximately 50 psi O2/Ar (5 mole % O2) gas mixture to the autoclaves for approximately 30 seconds. The polymerizations were quenched based on a predetermined pressure loss (quench value) of approximately 12 psid pressure loss or for a maximum of 45 minutes polymerization time. The reactors were cooled and vented. The polymer was isolated after the solvent was removed in-vacuo. The quench times are reported in Table 5 for each run. Yields reported include total weight of polymer and residual catalyst. Catalyst activity is reported as grams of polymer per mmol transition metal compound per hour of reaction time (g/mmol·hr). Propylene polymerization examples and ethylene/propylene copolymerization examples are collected in Table 5.

Polymer Characterization

For analytical testing, polymer sample solutions were prepared by dissolving polymer in 1,2,4-trichlorobenzene (TCB, 99+% purity from Sigma-Aldrich) containing 2,6-di-tert-butyl-4-methylphenol (BHT, 99% from Aldrich) at 165° C. in a shaker oven for approximately 3 hours. The typical concentration of polymer in solution was between 0.1 to 0.9 mg/mL with a BHT concentration of 1.25 mg BHT/mL of TCB. Samples were cooled to 135° C. for testing.

High temperature size exclusion chromatography was performed using an automated “Rapid GPC” system as described in U.S. Pat. Nos. 6,491,816; 6,491,823; 6,475,391; 6,461,515; 6,436,292; 6,406,632; 6,175,409; 6,454,947; 6,260,407; and 6,294,388; each of which is incorporated herein by reference. Molecular weights (weight average molecular weight (Mw) and number average molecular weight (Mn)) and molecular weight distribution (MWD=Mw/Mn), which is also sometimes referred to as the polydispersity (PDI) of the polymer, were measured by Gel Permeation Chromatography using a Symyx Technology GPC equipped with evaporative light scattering detector (ELSD) and calibrated using polystyrene standards (Polymer Laboratories: Polystyrene Calibration Kit S-M-10: Mp (peak Mw) between 5000 and 3,390,000). Alternatively, samples were measured by Gel Permeation Chromatography using a Symyx Technology GPC equipped with dual wavelength infrared detector and calibrated using polystyrene standards (Polymer Laboratories: Polystyrene Calibration Kit S-M-10: Mp (peak Mw) between 580 and 3,039,000). Samples (250 μL of a polymer solution in TCB were injected into the system) were run at an eluent flow rate of 2.0 mL/minute (135° C. sample temperatures, 165° C. oven/columns) using three Polymer Laboratories: PLgel 10 μm Mixed-B 300×7.5 mm columns in series. No column spreading corrections were employed. Numerical analyses were performed using Epoch® software available from Symyx Technologies or Automation Studio software available from Freeslate. The molecular weights obtained are relative to linear polystyrene standards. Molecular weight data is reported in Tables 1, 2, 3 and 5 under the headings Mn, Mw and PDI as defined above. PDI values marked with an “{circumflex over ( )}” indicate that the dual wavelength infrared detector was used; no additional marking indicates that the ELSD was used.

Differential Scanning Calorimetry (DSC) measurements were performed on a TA-Q100 instrument to determine the melting point of the polymers. Samples were pre-annealed at 220° C. for 15 minutes and then allowed to cool to room temperature overnight. The samples were then heated to 220° C. at a rate of 100° C./minute and then cooled at a rate of 50° C./minute. Melting points were collected during the heating period. The results are reported in the Tables 1, 2, 3, and 5 under the heading, Tm (° C.).

Samples for infrared analysis were prepared by depositing the stabilized polymer solution onto a silanized wafer (Part number S10860, Symyx). By this method, approximately between 0.12 and 0.24 mg of polymer is deposited on the wafer cell. The samples were subsequently analyzed on a Brucker Equinox 55 FTIR spectrometer equipped with Pikes' MappIR specular reflectance sample accessory. Spectra, covering a spectral range of 5000 cm⁻¹ to 500 cm⁻¹, were collected at a 2 cm⁻¹ resolution with 32 scans.

For ethylene-1-octene copolymers, the wt % octene in the copolymer was determined via measurement of the methyl deformation band at ˜1375 cm⁻¹. The peak height of this band was normalized by the combination and overtone band at ˜4321 cm⁻¹, which corrects for path length differences. The normalized peak height was correlated to individual calibration curves from ¹H NMR data to predict the wt % octene content within a concentration range of ˜2 to 35 wt % for octene. Typically, R² correlations of 0.98 or greater are achieved. These numbers are reported in Table 2 under the heading C8 (wt %).

For ethylene-propylene copolymers, the wt % ethylene is determined via measurement of the methylene rocking band (˜770 cm⁻¹ to 700 cm⁻¹). The peak area of this band is normalized by sum of the band areas of the combination and overtone bands in the 4500 cm⁻¹ to 4000 cm⁻¹ range. The normalized band area is then correlated to a calibration curve from ¹³C NMR data to predict the wt. % ethylene within a concentration range of ˜5 to 50 wt. %. Typically, R² correlations of 0.98 or greater are achieved. These numbers are reported in Table 5 under the heading C2 (wt %).

For some samples, polymer end-group analysis was determined by ¹H NMR using a Varian Unity+400 MHz instrument run with a single 300 flip angle, RF pulse. 120 pulses with a delay of 8 seconds between pulses were signal averaged. The polymer sample was dissolved in heated d₂-1,1,2,2-tetrachloroethane and signal collection took place at 120° C. Vinylenes were measured as the number of vinylenes per 1000 carbon atoms using the resonances between 5.55-5.31 ppm. Trisubstituted end-groups (“trisubs”) were measured as the number of trisubstituted groups per 1000 carbon atoms using the resonances between 5.30-5.11 ppm, by difference from vinyls. Vinyl end-groups were measured as the number of vinyls per 1000 carbon atoms using the resonances between 5.9-5.65 and between 5.13-4.98 ppm. Vinylidene end-groups were measured as the number of vinylidenes per 1000 carbon atoms using the resonances between 4.88-4.69 ppm. The values reported in Table 4 are % vinylene, % trisubstituted (% trisub), % vinyl and % vinylidene where the percentage is relative to the total olefinic unsaturation per 1000 carbon atoms.

¹³C NMR spectroscopy was used to characterize some polypropylene polymer samples produced in experiments collected in Table 3. This data is collected in Table 5. Unless otherwise indicated the polymer samples for ¹³C NMR spectroscopy were dissolved in d₂-1,1,2,2-tetrachloroethane and the samples were recorded at 125° C. using a NMR spectrometer with a ¹³C NMR frequency of 150 MHz. Polymer resonance peaks are referenced to mmmm=21.8 ppm. Calculations involved in the characterization of polymers by NMR follow the work of F. A. Bovey in “Polymer Conformation and Configuration,” Academic Press, New York 1969 and J. Randall in “Polymer Sequence Determination, Carbon-13 NMR Method,” Academic Press, New York, 1977.

The stereo defects measured as “stereo defects/10,000 monomer units” are calculated from the sum of the intensities of mmrr, mmrm+rrmr, and rmrm resonance peaks times 5000. The intensities used in the calculations are normalized to the total number of monomers in the sample. Methods for measuring 2,1 regio defects/10,000 monomers and 1,3 regio defects/10,000 monomers follow standard methods. Additional references include Grassi, A. et al. Macromolecules, 1988, 21, 617-622 and Busico et al. Macromolecules, 1994, 27, 7538-7543. The average meso run length=10000/[(stereo defects/10000 C)+(2,1-regio defects/10000 C)+(1,3-regio-defects/10000 C)].

Polymerization results are collected in Tables 1, 2, 3, 4, and 5 below. “Ex #” stands for example number. Under the Ex #column heading, the following abbreviations are defined: PE=polyethylene, EO=ethylene-1-octene copolymer, PP=polypropylene, EP=ethylene-propylene copolymer, CPE=comparative polyethylene, CEO=comparative ethylene-1-octene copolymer, CPP=comparative polypropylene, and CEP=comparative ethylene-propylene copolymer. Examples starting with a “C” as in CPP and CPE are comparative examples. “Cat ID” identifies the pre-catalyst used in the experiment. Corresponding letters identifying the pre-catalyst are located in the synthetic experimental section or below for comparative pre-catalysts. “Cat (μmol)” is the amount of pre-catalyst added to the reactor. For all experiments using dimethylanilinium tetrakisperfluorophenylborate (Act ID=2) or dimethylanilinium tetrakisperfluoronaphthylborate (Act ID=3), the molar ratio of activator/pre-catalyst was 1.1. For all experiments using MAO (Act ID=1) as the activator, a 500 Al/M molar ratio was used. T(° C.) is the polymerization temperature which was typically maintained within +/−1° C. “Yield” is polymer yield, and is not corrected for catalyst residue. “Quench time (s)” is the actual duration of the polymerization run in seconds. “Quench Value (psid)” for ethylene based polymerization runs (no propylene) is the set maximum amount of ethylene uptake (conversion) for the experiment. If a polymerization quench time is less than the maximum time set, then the polymerization ran until the set maximum value of ethylene uptake was reached. For propylene homopolymerization runs and ethylene-propylene copolymerization runs, quench value indicates the maximum set pressure loss (conversion) of propylene (for PP runs) or ethylene and propylene combined (for EP runs) during the polymerization. Activity is reported at grams polymer per mmol of catalyst per hour.

Comparative catalysts for polymerization runs include:

-   rac-Me₂Si[2,4-Me₂Ind]₂ZrCl₂—comparative pre-catalyst C-1 (Cat     ID=C-1); -   rac-Me₂Si(2-Me-4-EtInd)₂ZrCl₂—comparative pre-catalyst C-2 (Cat     ID=C-2); -   rac-Me₂Si(2,4-Me₂Ind)₂HfCl₂—comparative pre-catalyst C-3 (Cat     ID=C-3); -   rac-Me₂Si(2-Me-4-EtInd)₂HfCl₂—comparative pre-catalyst C-4 (Cat     ID=C-4); -   rac-(CH₂)₄Si[2,4-Me2Ind]₂HfCl₂—comparative pre-catalyst C-5 (Cat     ID=C-5); -   rac-(CH₂)₄Si[2-Me-4-EtInd]₂HfCl₂—comparative pre-catalyst C-6 (Cat     ID=C-6); -   rac-Me₂Si[2-MeInd]₂ZrCl₂—comparative pre-catalyst C-7 (Cat ID=C-7); -   rac-Me₂Si[2-MeInd]₂ZrMe₂—comparative pre-catalyst C-8 (Cat ID=C-8); -   rac-(CH₂)₄Si[2-Et-4-MeInd]2HfCl₂—comparative pre-catalyst C-9 (Cat     ID=C-9); and -   rac-(CH₂)₄Si[2,4-Et₂Ind]₂HfCl₂—comparative pre-catalyst C-10 (Cat     ID=C-10); -   where Ind is inden-1-yl and (CH₂)₄Si is silolanediyl (also called     cyclotetramethylenesilylene).

Polydispersity index (PDI) is defined to be Mw/Mn.

TABLE 1 Ethylene polymerization examples quench Activity Cat Act time yield (g P/mmol Mn Mw Tm Ex# ID ID (s) (g) cat · hr) (g/mol) (g/mol) PDI (° C.) PE-1 A 1 14 0.0774 813,547 325,462 535,075 1.64 135.9 PE-2 A 1 63 0.0941 216,806 352,585 586,832 1.66 134.1 PE-3 A 1 64 0.0958 217,247 407,129 646,034 1.59 133.6 PE-4 B 2 54 0.1009 269,566 315,978 562,136 1.78 135.7 PE-5 B 2 70 0.0962 199,321 333,501 590,895 1.77 135.2 PE-6 B 2 59 0.0940 228,649 411,942 672,628 1.63 135.4 PE-7 B 1 91 0.0989 156,846 332,543 544,471 1.64 133.8 PE-8 B 1 75 0.0975 187,952 384,321 698,852 1.82 134.9 PE-9 B 1 69 0.0955 200,466 331,997 555,096 1.67 134.2 PE-10 C 1 238 0.0847 51,333 825,734 1,458,366 1.77 134.7 PE-11 C 1 283 0.0861 43,842 PE-12 C 1 153 0.0828 78,134 875,659 1,538,837 1.76 134.4 PE-13 D 2 59 0.0904 221,765 759,705 2,490,105 3.28 135.8 PE-14 D 2 77 0.0869 161,884 1,134,775 2,087,024 1.84 133.3 PE-15 D 2 65 0.0935 207,458 1,169,367 2,142,344 1.83 135.3 PE-16 D 1 143 0.0914 91,911 616,009 1,175,848 1.91 141.7 PE-17 D 1 272 0.0907 48,053 703,568 1,279,609 1.82 133.9 PE-18 D 1 252 0.0923 52,764 720,328 1,282,451 1.78 134.7 PE-19 E 1 148 0.1005 97,652 617,808 1,156,018 1.87 135.9 PE-20 E 1 309 0.0895 41,655 760,749 1,490,739 1.96 134.9 PE-21 E 1 255 0.0914 51,553 657,812 1,234,986 1.88 135.6 PE-22 F 1 274 0.0841 44,279 454,535 792,712 1.74 136.1 PE-23 F 1 233 0.0798 49,425 463,924 808,167 1.74 136.9 PE-24 F 1 207 0.0796 55,267 PE-25 G 1 850 0.0313 5,301 137,172 1,496,705 10.91 134.3 PE-26 G 1 931 0.0325 5,026 132,676 1,581,538 11.92 134.1 PE-27 G 1 745 0.0312 6,030 123,526 1,519,633 12.30 134.3 PE-28 H 1 146 0.0858 84,857 PE-29 H 1 197 0.0891 65,060 275,641 548,103 1.99 137.4 PE-30 H 1 136 0.0847 89,485 PE-31 I 1 386 0.0332 12,373 151,795 569,163 3.75 134.5 PE-32 I 1 454 0.0332 10,537 141,673 551,944 3.90 133.7 PE-33 I 1 376 0.0327 12,530 151,763 572,743 3.77 134.6 PE-34 J 2 77 0.0825 154,286 195,565 531,085 2.72 135.4 PE-35 J 2 83 0.0808 140,183 69,412 555,118 8.00 137.8 PE-36 J 2 74 0.0821 158,903 194,052 531,692 2.74 135.7 PE-37 J 1 85 0.0823 140,085 297,837 521,056 1.75 133.4 PE-38 J 1 84 0.0816 140,723 323,365 563,313 1.74 136.1 PE-39 J 1 97 0.0834 123,683 323,349 540,937 1.67 133.6 PE-40 K* 2 153 0.0926 86,926 668,752 953,293 1.43 135.6 PE-41 K* 2 146 0.0845 83,571 523,709 798,243 1.52 134.3 PE-42 K* 2 177 0.0869 70,658 603,439 930,122 1.54 136.5 PE-43 K 1 102 0.1051 147,797 514,968 957,928 1.86 134.8 PE-44 K 1 112 0.0982 126,823 469,186 946,840 2.02 134.1 PE-45 K 1 96 0.1065 159,418 492,576 1,004,014 2.04 134.7 PE-46 L* 2 81 0.0863 158,127 1,330,594 2,445,401 1.84 135.8 PE-47 L* 2 57 0.0866 226,840 1,222,485 2,235,291 1.83 134.2 PE-48 L* 2 43 0.0879 301,335 1,181,677 2,096,612 1.77 135.6 PE-49 L 1 231 0.0828 53,281 585,251 1,174,374   2.01{circumflex over ( )} 134.8 PE-50 L 1 232 0.0853 54,630 682,245 1,252,199   1.84{circumflex over ( )} 135.1 PE-51 L 1 247 0.0850 51,138 657,496 1,238,802   1.88{circumflex over ( )} 134.2 Total solvent volume: 5.0 ml toluene; 0.025 μmol pre-catalyst for examples PE-1 through PE-46; 0.024 μmol pre-catalyst for examples PE-46 through PE-51; Quench Value was set at 20 psid ethylene uptake. *Pre-catalysts were pre-alkylated with 0.5 μmol of triisobutyl aluminum prior to injection into the reactor. {circumflex over ( )}GPC data from dual wavelength infrared detector used with Automation Studio software.

TABLE 2 Ethylene-1-octene copolymerization examples quench Activity Cat Act Pressure time yield (g P/mmol Mn Mw C8 Tm Ex# ID ID (psig) (s) (g) cat · hr) (g/mol) (g/mol) PDI (wt %) (° C.) EO-1 A 1 75 41 0.1052 374,044 193,791 333,558 1.72 20.6 102.0 EO-2 A 1 75 48 0.1149 343,270 172,913 320,715 1.85 20.3 108.9 EO-3 A 1 75 49 0.4140 1,219,141 172,459 323,262 1.87 21.3 109.5 EO-4 A 1 200 36 0.1959 783,600 212,901 359,220 1.69 7.4 121.5 EO-5 A 1 200 45 0.2006 643,350 215,835 389,440 1.80 8.0 120.9 EO-6 A 1 200 43 0.2063 695,719 197,190 349,667 1.77 10.3 120.7 EO-7 B 1 75 45 0.1183 375,225 159,648 309,349 1.94 23.3 108.2 EO-8 B 1 75 44 0.1229 400,398 160,750 314,095 1.95 21.0 108.3 EO-9 B 1 75 43 0.1164 389,805 156,159 309,900 1.98 20.8 107.8 EO-10 B 1 200 37 0.2053 803,348 191,162 331,733 1.74 9.2 120.7 EO-11 B 1 200 37 0.2027 788,886 200,830 340,123 1.69 9.0 120.6 EO-12 B 1 200 36 0.2018 809,448 197,929 337,435 1.70 9.3 120.7 EO-13 B 2 75 41 0.1144 405,754 131,835 264,289 2.00 21.4 109.5 EO-14 B 2 75 40 0.1166 422,932 137,620 267,195 1.94 21.9 108.4 EO-15 B 2 75 38 0.1185 453,830 127,688 266,936 2.09 21.8 110.2 EO-16 B 2 200 27 0.1915 1,040,604 172,971 293,025 1.69 7.3 122.2 EO-17 B 2 200 37 0.2045 802,398 177,924 297,958 1.67 7.0 121.7 EO-18 B 2 200 34 0.2018 852,176 173,428 290,375 1.67 7.7 121.8 EO-19 C 1 75 116 0.0750 93,345 428,305 760,892 1.78 17.0 109.2 EO-21 C 1 75 118 0.0814 99,000 424,104 747,317 1.76 18.6 108.2 EO-22 C 1 200 125 0.1831 210,426 353,003 752,818 2.13 13.6 116.4 EO-23 C 1 200 114 0.1843 233,209 385,833 818,606 2.12 12.3 116.8 EO-24 C 1 200 110 0.1809 235,957 395,743 848,736 2.14 12.0 116.2 EO-25 D 1 75 136 0.0621 65,850 390,784 672,716 1.72 17.3 108.7 EO-26 D 1 75 134 0.0966 104,042 368,016 677,095 1.84 20.3 109.1 EO-27 D 1 75 105 0.0899 123,881 381,342 695,131 1.82 21.1 109.4 EO-28 D 1 200 93 0.1845 287,222 326,354 637,179 1.95 9.3 118.6 EO-29 D 1 200 127 0.1928 218,093 333,835 735,238 2.20 12.6 117.3 EO-30 D 1 200 128 0.2025 227,457 324,842 714,491 2.20 12.6 118.2 EO-31 D 2 75 146 0.1413 139,556 101,830 748,129 7.35 33.3 108.5 EO-32 D 2 75 167 0.1467 126,723 116,718 543,345 4.66 36.3** 101.8 EO-33 D 2 75 102 0.1375 194,882 109,411 701,351 6.41 32.8 107.6 EO-34 D 2 200 41 0.2161 753,472 68,447 1,079,001 15.76 21.6 100.1 EO-35 D 2 200 38 0.2219 852,096 58,226 986,781 16.95 22.6 99.8 EO-36 E 1 75 122 0.0636 75,007 436,418 719,009 1.65 11.2 110.4 EO-37 E 1 75 145 0.1027 102,274 351,200 711,031 2.02 21.5 107.2 EO-38 E 1 75 110 0.0783 102,876 420,857 700,468 1.66 13.7 109.4 EO-39 E 1 200 107 0.1838 247,126 370,293 748,712 2.02 8.1 118.1 EO-40 E 1 200 130 0.1930 213,456 307,148 842,951 2.74 12.8 116.2 EO-41 E 1 200 133 0.1901 206,599 330,605 787,487 2.38 9.5 117.0 EO-42 F 1 75 71 0.0866 175,887 238,315 473,537 1.99 8.4 113.3 EO-43 F 1 75 68 0.0845 178,678 241,929 460,146 1.90 8.9 113.2 EO-44 F 1 75 76 0.0883 167,085 232,102 466,510 2.01 9.2 113.9 EO-45 F 1 200 97 0.1776 262,841 224,333 607,992 2.71 6.4 121.4 EO-46 F 1 200 105 0.1756 241,744 238,660 595,437 2.49 6.9 121.3 EO-47 F 1 200 104 0.1750 243,478 EO-48 G 1 75 261 0.0334 18,421 103,015 189,351 1.84 8.0 113.6 EO-49 G 1 75 368 0.0352 13,774 87,238 183,316 2.10 8.1 113.3 EO-50 G 1 75 231 0.0321 19,976 103,287 186,866 1.81 9.0 112.8 EO-51 G 1 200 79 0.0433 79,328 196,785 389,660 1.98 4.6 122.8 EO-52 G 1 200 86 0.0463 77,979 205,313 403,146 1.96 4.5 122.5 EO-53 G 1 200 81 0.0431 76,246 198,888 390,929 1.97 4.0 122.8 EO-54 H 1 75 64 0.0869 194,613 134,375 252,272 1.88 19.3 85.7 EO-55 H 1 75 60 0.0764 182,448 154,414 258,243 1.67 18.3 88.2 EO-56 H 1 75 54 0.0810 214,412 EO-57 H 1 200 180 0.1908 152,895 125,188 398,280 3.18 14.3 106.5 EO-58 H 1 200 156 0.1979 182,443 84,470 384,898 4.56 13.8 108.3 EO-59 H 1 200 156 0.1648 151,734 48,359 176,309 3.65 19.2 105.9 EO-60 I 1 75 701 0.0349 7,165 73,955 137,813 1.86 12.2 110.2 EO-61 I 1 75 611 0.0360 8,490 71,881 241,910 3.37 12.1 110.4 EO-62 I 1 75 643 0.0352 7,882 68,513 227,939 3.33 12.1 111.3 EO-63 I 1 200 136 0.0439 46,482 212,809 393,502 1.85 5.8 118.6 EO-64 I 1 200 156 0.0445 40,972 201,650 482,275 2.39 5.8 119.4 EO-65 I 1 200 116 0.0413 51,181 198,929 442,800 2.23 6.5 118.7 EO-66 J 1 75 61 0.0870 204,039 127,730 219,381 1.72 19.9 85.4 EO-67 J 1 75 60 0.0844 201,552 138,064 227,995 1.65 19.8 86.4 EO-68 J 1 75 58 0.0880 218,107 130,502 225,577 1.73 20.2 84.8 EO-69 J 1 200 156 0.2073 190,987 297,003 606,149 2.04 12.1 109.7 EO-70 J 1 200 148 0.1991 193,197 83,350 355,471 4.26 13.7 107.5 EO-71 J 1 200 143 0.2015 203,193 79,211 346,478 4.37 14.6 108.0 EO-72 J 2 75 43 0.1055 354,126 48,896 135,384 2.77 25.0 85.6 EO-73 J 2 75 44 0.1089 354,787 51,311 146,735 2.86 22.4 86.3 EO-74 J 2 75 44 0.1107 359,027 49,634 154,012 3.10 22.0 84.7 EO-75 J 2 200 99 0.2006 293,263 25,289 484,587 19.16 13.6 111.1 EO-76 J 2 200 100 0.1958 282,234 36,948 510,452 13.82 14.2 110.8 EO-77 J 2 200 95 0.1938 292,835 222,803 550,149 2.47 14.4 110.9 EO-78 K 1 75 72 0.1278 257,028 155,379 452,281 2.91 30.3 104.5 EO-79 K 1 75 89 0.1224 197,375 126,721 453,729 3.58 27.3 106.4 EO-80 K 1 75 89 0.1303 211,536 103,684 380,130 3.67 34.6 104.8 EO-81 K 1 200 51 0.2123 599,435 125,238 531,427 4.24 12.7 116.9 EO-82 K 1 200 58 0.1639 408,332 100,848 483,989 4.80 14.6 116.3 EO-83 K 1 200 55 0.1983 522,989 114,143 530,861 4.65 13.1 117.1 EO-84 K* 2 75 54 0.1008 269,799 238,859 371,814 1.56 21.2 99.4 EO-85 K* 2 75 76 0.0943 177,971 303,826 461,470 1.52 17.6 102.7 EO-86 K* 2 75 74 0.0939 182,232 308,678 453,374 1.47 16.2 104.3 EO-87 K* 2 200 114 0.1850 233,071 291,119 465,357 1.60 11.5 117.6 EO-88 K* 2 200 122 0.1868 221,393 306,238 482,540 1.58 10.4 117.8 EO-89 K* 2 200 118 0.1957 238,618 280,052 460,833 1.65 11.6 118.1 EO-90 L 1 75 152 0.0606 59,200 478,005 817,488   1.71{circumflex over ( )} 13.8 105.5 EO-91 L 1 75 146 0.0590 59,960 422,444 757,024   1.79{circumflex over ( )} 14.3 105.1 EO-92 L 1 75 150 0.0588 58,245 463,583 824,663   1.78{circumflex over ( )} 15.3 105.1 EO-93 L 1 200 153 0.1667 162,105 449,047 873,852   1.95{circumflex over ( )} 9.7 113.7 EO-94 L 1 200 143 0.1637 170,797 457,542 871,130   1.90{circumflex over ( )} 9.7 114.1 EO-95 L 1 200 140 0.1671 177,329 421,602 844,930   2.00{circumflex over ( )} 10.6 114.4 EO-96 L* 2 75 249 0.1246 74,331 248,820 512,382 2.06 34.4 100.3 EO-97 L* 2 75 164 0.1227 111,655 252,341 520,920 2.06 32.4 EO-98 L* 2 75 224 0.1213 80,604 297,124 586,696 1.97 31.0 99.7 EO-99 L* 2 200 87 0.2022 344,602 305,672 927,970 3.04 21.9 111.8 EO-100 L* 2 200 96 0.1941 301,762 204,422 646,982 3.16 23.3 110.7 EO-101 L* 2 200 87 0.1933 330,191 268,116 723,459 2.70 21.7 110.9 Total solvent volume: 4.9 ml toluene; 0.025 μmol pre-catalyst for examples EO-1 through EO-89; 0.024 μmol pre-catalyst for examples EO-90 through EO-101; Quench Value was set at 20 psid ethylene uptake if 75 psid ethylene pressure was used, or 15 psid eithylene uptake if 200 psid ethylene pressure was used *Pre-catalysts were pre-alkylated with 0.5 μmol of triisobutyl aluminum prior to injection into the reactor {circumflex over ( )}GPC data from dual wavelength infrared detector used with Automation Studio software **Outside calibration range

TABLE 3 Propylene polymerization examples Quench quench Activity Cat Act Cat Isohexane Toluene value time yield (g P/mmol Mn Mw Tm Ex# ID ID (μmol) (uL) (uL) T (C) (psi) (s) (g) cat · hr) (g/mol) (g/mol) PDI (° C.) PP-1 A 1 0.040 3841 258 70 20 109 0.2222 184,313 52,101 89,804 1.72 151.0 PP-2 A 1 0.040 3841 258 70 20 120 0.3208 240,600 51,152 90,217 1.76 151.2 PP-3 A 1 0.040 3841 258 70 20 113 0.3072 244,240 55,793 95,130 1.71 151.5 PP-4 A 1 0.025 3882 217 70 15 144 0.2365 236,172 73,447 123,855 1.69 152.4 PP-5 A 1 0.025 3882 217 70 15 154 0.2515 235,322 70,881 118,539 1.67 150.9 PP-6 A 1 0.025 3882 217 70 15 149 0.2442 236,323 68,263 115,775 1.70 151.9 PP-7 A 1 0.040 3841 258 100 20 91 0.2633 261,268 18,656 33,646 1.80 143.6 PP-8 A 1 0.040 3841 258 100 20 89 0.2390 242,503 17,895 32,404 1.81 143.5 PP-9 A 1 0.040 3841 258 100 20 93 0.2382 229,775 18,236 32,576 1.79 143.6 PP-10 A 1 0.025 3882 217 100 15 135 0.1912 203,645 26,221 42,028 1.60 145.4 PP-11 A 1 0.025 3882 217 100 15 156 0.1766 162,807 24,460 39,109 1.60 144.3 PP-12 A 1 0.025 3882 217 100 15 125 0.1848 213,060 27,573 44,858 1.63 145.0 PP-13 B 1 0.040 3841 258 70 20 114 0.2950 232,487 58,122 98,129 1.69 151.8 PP-14 B 1 0.040 3841 258 70 20 128 0.3129 219,493 53,957 94,821 1.76 151.3 PP-15 B 1 0.040 3841 258 70 20 131 0.2315 159,046 50,352 91,141 1.81 151.0 PP-16 B 1 0.025 3882 217 70 15 135 0.2226 237,440 69,534 116,726 1.68 151.6 PP-17 B 1 0.025 3882 217 70 15 143 0.2418 244,174 65,840 112,580 1.71 152.0 PP-18 B 1 0.025 3882 217 70 15 154 0.2635 246,390 65,167 112,986 1.73 152.6 PP-19 B 1 0.040 3841 258 100 20 92 0.1952 191,164 19,120 34,416 1.80 143.5 PP-20 B 1 0.040 3841 258 100 20 97 0.2577 239,103 18,313 33,695 1.84 143.6 PP-21 B 1 0.040 3841 258 100 20 88 0.2322 238,562 19,764 34,915 1.77 143.6 PP-22 B 1 0.025 3882 217 100 15 145 0.1839 182,632 27,965 44,103 1.58 144.9 PP-23 B 1 0.025 3882 217 100 15 135 0.1826 194,773 28,340 46,043 1.62 146.1 PP-24 B 1 0.025 3882 217 100 15 159 0.1666 150,978 31,064 47,987 1.54 146.1 PP-25 B 2 0.040 3832 268 70 15 53 0.3093 528,216 24,210 53,428 2.21 149.4 PP-26 B 2 0.040 3832 268 70 15 51 0.3518 624,497 19,024 49,192 2.59 149.3 PP-27 B 2 0.040 3832 268 70 15 42 0.2988 643,349 20,741 49,957 2.41 148.7 PP-28 B 2 0.040 3832 268 70 15 45 0.2899 582,388 19,983 51,210 2.56 148.6 PP-29 B 2 0.040 3832 268 70 15 43 0.3644 760,928 20,703 50,095 2.42 148.6 PP-30 B 2 0.040 3832 268 100 15 64 0.2334 329,765 9,839 19,203 1.95 141.8 PP-31 B 2 0.040 3832 268 100 15 49 0.2637 483,360 7,010 15,692 2.24 139.1 PP-32 B 2 0.040 3832 268 100 15 51 0.2626 466,154 8,785 17,972 2.05 140.3 PP-33 B 2 0.040 3832 268 100 15 51 0.2762 483,619 7,943 16,360 2.06 140.8 PP-34 B 2 0.040 3832 268 100 15 52 0.2588 452,272 7,958 16,752 2.11 140.3 PP-35 C 1 0.040 3841 258 70 20 1534 0.1743 10,229 140,365 238,564 1.70 155.8 PP-36 C 1 0.040 3841 258 70 20 1371 0.1788 11,739 130,479 219,647 1.68 157.1 PP-37 C 1 0.040 3841 258 70 20 1671 0.1787 9,624 139,454 232,168 1.66 156.4 PP-38 C 1 0.040 3841 258 100 20 794 0.1452 16,461 33,798 54,318 1.61 148.8 PP-39 C 1 0.040 3841 258 100 20 820 0.1508 16,543 31,327 50,410 1.61 149.1 PP-40 C 1 0.040 3841 258 100 20 1007 0.1400 12,519 30,639 49,987 1.63 148.1 PP-41 D 1 0.040 3841 258 70 20 1801 0.1345 6,720 132,051 222,181 1.68 156.7 PP-42 D 1 0.040 3841 258 70 20 1311 0.1746 11,991 140,413 224,113 1.60 157.1 PP-43 D 1 0.040 3841 258 70 20 1507 0.1731 10,339 129,064 216,542 1.68 157.4 PP-44 D 1 0.040 3841 258 100 20 768 0.1350 15,820 31,078 49,172 1.58 149.3 PP-45 D 1 0.040 3841 258 100 20 859 0.1228 12,869 27,928 44,269 1.59 147.6 PP-46 D 1 0.040 3841 258 100 20 892 0.1361 13,727 32,830 53,208 1.62 149.9 PP-47 D 2 0.040 3832 268 70 15 33 0.2860 784,756 12,590 52,397 4.16 145.4 PP-48 D 2 0.040 3832 268 70 15 73 0.3326 411,747 30,928 77,319 2.50 150.0 PP-49 D 2 0.040 3832 268 70 15 48 0.3202 599,127 28,117 74,382 2.65 149.2 PP-50 D 2 0.040 3832 268 70 15 35 0.3216 831,724 13,004 53,321 4.10 145.8 PP-51 D 2 0.040 3832 268 70 15 37 0.2422 584,397 17,385 66,765 3.84 147.6 PP-52 D 2 0.040 3832 268 70 15 41 0.3325 733,456 15,497 63,594 4.10 147.3 PP-53 D 2 0.040 3832 268 100 15 73 0.1940 240,165 13,929 27,321 1.96 143.1 PP-54 D 2 0.040 3832 268 100 15 1802 0.0000 PP-55 D 2 0.040 3832 268 100 15 24 0.2676 1,024,851 6,029 17,041 2.83 137.2 PP-56 D 2 0.040 3832 268 100 15 27 0.3185 1,065,613 5,905 17,710 3.00 138.1 PP-57 D 2 0.040 3832 268 100 15 24 0.3047 1,152,227 7,951 20,891 2.63 139.8 PP-58 D 2 0.040 3832 268 100 15 25 0.3005 1,073,214 5,740 15,302 2.67 137.0 PP-59 E 1 0.040 0 4099 70 15 586 0.1320 20,266 117,061 193,977 1.66 156.4 PP-60 E 1 0.040 0 4099 70 15 649 0.1319 18,302 121,768 202,573 1.66 156.4 PP-61 E 1 0.040 0 4099 70 15 535 0.1281 21,541 124,933 207,468 1.66 156.9 PP-62 E 1 0.040 0 4099 100 15 530 0.1052 17,854 29,729 48,263 1.62 148.6 PP-63 E 1 0.040 0 4099 100 15 747 0.1079 13,005 30,558 49,866 1.63 148.8 PP-64 E 1 0.040 0 4099 100 15 743 0.0989 11,988 28,482 45,997 1.61 148.6 PP-65 F 1 0.040 3841 258 70 20 1802 0.0468 2,337 6,910 10,345 1.50 143.8 PP-66 F 1 0.040 3841 258 70 20 1800 0.0563 2,814 8,845 13,614 1.54 145.7 PP-67 F 1 0.040 3841 258 70 20 1802 0.0550 2,746 9,033 13,868 1.54 145.7 PP-68 F 1 0.080 0 4098 70 15 1800 0.0862 2,155 6,178 9,855 1.60 143.5 PP-69 F 1 0.080 0 4098 70 15 1802 0.0866 2,162 6,102 9,744 1.60 143.5 PP-70 F 1 0.080 0 4098 70 15 1800 0.0879 2,197 6,081 9,674 1.59 142.8 PP-71 F 1 0.040 3841 258 100 20 1801 0.0714 3,567 2,010 2,393 1.19 120.7 PP-72 F 1 0.040 3841 258 100 20 1802 0.0720 3,597 1,976 2,349 1.19 120.3 PP-73 F 1 0.040 3841 258 100 20 1802 0.0712 3,556 1,946 2,293 1.18 118.0 PP-74 F 1 0.080 0 4098 100 15 1332 0.0885 2,990 1,608 1,878 1.17 111.4 PP-75 F 1 0.080 0 4098 100 15 1317 0.0714 2,440 1,570 1,791 1.14 136.2 PP-76 F 1 0.080 0 4098 100 15 1360 0.0900 2,978 1,651 1,951 1.18 112.1 PP-77 G 1 0.040 3841 258 70 20 1802 0.0422 2,108 2,791 3,661 1.31 PP-78 G 1 0.040 3841 258 70 20 1801 0.0466 2,329 3,135 4,209 1.34 PP-79 G 1 0.040 3841 258 70 20 1802 0.0458 2,288 2,942 3,901 1.33 PP-80 G 1 0.040 3841 258 100 20 1801 0.0246 1,229 PP-81 G 1 0.040 3841 258 100 20 1802 0.0221 1,104 1,414 1,498 1.06 PP-82 G 1 0.040 3841 258 100 20 1801 0.0181 905 1,414 1,488 1.05 PP-83 H 1 0.040 3841 258 70 20 1800 0.1187 5,935 9,723 15,762 1.62 147.6 PP-84 H 1 0.040 3841 258 70 20 1801 0.0858 4,287 11,437 17,130 1.50 148.0 PP-85 H 1 0.040 3841 258 70 20 1803 0.1129 5,636 9,885 16,118 1.63 148.5 PP-86 H 1 0.080 0 4098 70 15 518 0.1333 11,573 5,976 9,642 1.61 145.6 PP-87 H 1 0.080 0 4098 70 15 531 0.1360 11,534 6,361 10,302 1.62 144.8 PP-88 H 1 0.080 0 4098 70 15 613 0.1358 9,964 6,212 9,963 1.60 145.0 PP-89 H 1 0.040 3841 258 100 20 1801 0.0885 4,422 2,142 2,679 1.25 127.7 PP-90 H 1 0.040 3841 258 100 20 1801 0.0838 4,188 2,045 2,528 1.24 123.4 PP-91 H 1 0.040 3841 258 100 20 1802 0.0983 4,910 PP-92 H 1 0.080 0 4098 100 15 425 0.1069 11,313 1,718 2,052 1.19 119.0 PP-93 H 1 0.080 0 4098 100 15 432 0.1055 10,987 1,755 2,087 1.19 119.5 PP-94 H 1 0.080 0 4098 100 15 415 0.1031 11,171 1,682 1,986 1.18 108.9 PP-95 I 1 0.040 3841 258 70 15 1803 0.0282 1,408 9,903 81,880 8.27 142.0 PP-96 I 1 0.040 3841 258 70 15 1800 0.0093 465 PP-97 I 1 0.040 3841 258 70 15 1802 0.0087 435 PP-98 I 1 0.040 3841 258 100 15 1802 0.0324 1,618 11,185 19,621 1.75 138.2 PP-99 I 1 0.040 3841 258 100 15 1800 0.0091 455 PP-100 I 1 0.040 3841 258 100 15 1802 0.0057 285 PP-101 J 1 0.040 3841 258 70 15 1802 0.0876 4,376 11,172 17,637 1.58 149.6 PP-102 J 1 0.040 3841 258 70 15 1801 0.1058 5,288 9,842 16,125 1.64 148.5 PP-103 J 1 0.040 3841 258 70 15 1801 0.0952 4,758 10,158 16,399 1.61 149.5 PP-104 J 1 0.040 3841 258 100 15 1800 0.0688 3,440 1,999 2,429 1.21 124.4 PP-105 J 1 0.040 3841 258 100 15 1729 0.0629 3,274 1,963 2,353 1.20 121.8 PP-106 J 1 0.040 3841 258 100 15 1802 0.0857 4,281 2,149 2,675 1.24 126.9 PP-107 J 2 0.040 3832 268 70 15 1800 0.0103 515 7,038 11,251 1.60 144.5 PP-108 J 2 0.080 3664 436 70 15 525 0.1474 12,632 5,345 8,913 1.67 141.1 PP-109 J 2 0.080 3664 436 70 15 566 0.1575 12,513 7,276 11,334 1.56 143.4 PP-110 J 2 0.080 3664 436 70 15 540 0.1580 13,169 6,389 10,621 1.66 142.3 PP-111 J 2 0.040 3832 268 100 15 1800 0.0814 4,069 1,686 2,003 1.19 PP-112 J 2 0.040 3832 268 100 15 1002 0.0988 8,876 1,682 1,978 1.18 133.1 PP-113 J 2 0.040 3832 268 100 15 952 0.0997 9,429 1,635 1,927 1.18 115.1 PP-114 J 2 0.080 3664 436 100 15 460 0.1185 11,597 1,792 2,070 1.16 114.1 PP-115 J 2 0.080 3664 436 100 15 539 0.1163 9,717 1,776 2,058 1.16 114.1 PP-116 J 2 0.080 3664 436 100 15 472 0.1129 10,773 1,775 2,031 1.14 112.0 PP-117 K 1 0.025 0 4099 70 7.5 81 0.1950 348,387 83,658 127,890 1.53 154.4 PP-118 K 1 0.025 0 4099 70 7.5 104 0.1759 244,258 115,599 168,124 1.45 155.0 PP-119 K 1 0.025 0 4099 70 7.5 81 0.2335 416,654 88,240 136,224 1.54 154.5 PP-120 K 1 0.025 0 4099 100 7.5 83 0.1424 248,553 34,662 52,822 1.52 149.1 PP-121 K 1 0.025 0 4099 100 7.5 70 0.1592 327,966 31,889 49,196 1.54 148.0 PP-122 K 1 0.025 0 4099 100 7.5 68 0.1500 318,584 30,527 46,978 1.54 149.6 PP-123 L 1 0.077 0 4098 70 8 178 0.0970 25,365 92,027 139,402 1.51 156.0 PP-124 L 1 0.077 0 4098 70 8 181 0.1065 27,387 87,291 134,431 1.54 156.7 PP-125 L 1 0.077 0 4098 70 8 173 0.0961 25,857 89,890 138,573 1.54 155.6 PP-126 L 1 0.077 0 4098 70 8 163 0.1199 34,169 77,478 167,316   2.16{circumflex over ( )} 157.4 PP-127 L 1 0.077 0 4098 70 8 178 0.1211 31,659 78,594 171,709   2.18{circumflex over ( )} 157.4 PP-128 L 1 0.077 0 4098 70 8 161 0.1205 34,740 76,762 167,676   2.18{circumflex over ( )} 157.6 PP-129 L 1 0.077 0 4098 70 8 144 0.1266 40,820 80,609 172,695   2.14{circumflex over ( )} 156.4 PP-130 L 1 0.077 0 4098 70 8 159 0.1331 38,823 80,457 171,710   2.13{circumflex over ( )} 157.4 PP-131 L 1 0.077 0 4098 70 8 144 0.1297 41,877 77,938 168,273   2.16{circumflex over ( )} 156.6 PP-132 L 1 0.077 0 4098 100 8 151 0.1097 33,890 22,885 34,583 1.51 147.0 PP-134 L 1 0.077 0 4098 100 8 133 0.1056 36,805 23,378 35,340 1.51 147.4 PP-135 L 1 0.077 0 4098 100 8 160 0.1087 31,627 23,562 35,511 1.51 148.2 PP-136 L 1 0.077 0 4098 100 8 117 0.1191 47,471 22,461 43,702   1.95{circumflex over ( )} 147.6 PP-137 L 1 0.077 0 4098 100 8 123 0.1239 46,698 19,006 37,862   1.99{circumflex over ( )} 147.6 PP-138 L 1 0.077 0 4098 100 8 129 0.1178 42,372 20,636 40,109   1.94{circumflex over ( )} 147.8 PP-139 L 1 0.077 0 4098 100 8 114 0.1190 48,406 20,735 41,134   1.98{circumflex over ( )} 147.1 PP-140 L 1 0.077 0 4098 100 8 109 0.1166 49,965 19,406 38,727   2.00{circumflex over ( )} 148.3 PP-141 L 1 0.077 0 4098 100 8 117 0.1255 50,000 21,330 38,028   1.78{circumflex over ( )} 147.1 PP-142 D 2 0.020 3916 184 70 12 46.3 0.3091 1,201,685 29,459 71,088 2.41 145.9 PP-143 D 2 0.020 3916 184 70 12 43.4 0.3312 1,373,641 32,006 73,455 2.30 147.1 PP-144 D 2 0.020 3916 184 70 12 46 0.3296 1,289,739 27,672 69,298 2.50 146.9 PP-145 D 2 0.020 3916 184 100 12 40.4 0.2235 995,792 10,700 22,322 2.09 141.6 PP-146 D 2 0.020 3916 184 100 12 35.4 0.2611 1,327,627 9,133 20,571 2.25 138.0 PP-147 D 2 0.020 3916 184 100 12 32.8 0.2422 1,329,146 10,152 20,931 2.06 139.6 PP-148 D 3 0.020 3916 184 70 12 52.6 0.3099 1,060,494 49,650 117,199 2.36 150.2 PP-149 D 3 0.020 3916 184 70 12 58.5 0.3327 1,023,692 49,850 119,464 2.40 150.8 PP-150 D 3 0.020 3916 184 70 12 59.1 0.3412 1,039,188 47,150 114,711 2.43 151.3 PP-151 D 3 0.020 3916 184 100 12 45.2 0.2444 973,274 16,226 33,137 2.04 142.6 PP-152 D 3 0.020 3916 184 100 12 45 0.2087 834,800 18,082 34,617 1.91 143.3 PP-153 D 3 0.020 3916 184 100 12 49 0.2354 864,735 16,147 35,116 2.17 143.5 CPP-1 C-1 1 0.080 0 265 70 5 301 0.0521 7,783 66,393 110,301 1.66 138.5 CPP-2 C-1 1 0.080 0 265 70 5 324 0.0527 7,315 63,094 106,092 1.68 138.6 CPP-3 C-1 1 0.100 0 331 70 5 240 0.0624 9,353 64,138 112,805 1.76 134.9 CPP-4 C-1 1 0.100 0 331 70 5 222 0.0560 9,062 63,788 105,815 1.66 133.3 CPP-5 C-2 1 0.025 0 4099 70 7.5 162 0.0831 74,095 72,417 103,663 1.43 143.5 CPP-6 C-2 1 0.025 0 4099 70 7.5 176 0.1075 88,205 72,911 107,306 1.47 143.3 CPP-7 C-2 1 0.025 0 4099 70 7.5 154 0.0871 81,233 72,449 104,518 1.44 143.3 CPP-8 C-2 1 0.025 0 4099 100 7.5 125 0.0716 82,814 18,609 26,172 1.41 134.0 CPP-9 C-2 1 0.025 0 4099 100 7.5 134 0.0712 76,743 17,468 25,677 1.47 134.6 CPP-10 C-2 1 0.025 0 4099 100 7.5 139 0.0757 78,310 18,241 25,266 1.39 133.6 CPP-11 C-3 1 0.040 0 4099 70 8 1023 0.0608 5,348 55,738 81,650 1.46 151.8 CPP-12 C-3 1 0.040 0 4099 70 8 1162 0.0658 5,096 53,737 79,557 1.48 151.9 CPP-13 C-3 1 0.040 0 4099 70 8 1159 0.0611 4,744 57,491 83,420 1.45 152.1 CPP-14 C-3 1 0.040 0 4099 100 8 864 0.0549 5,720 13,601 19,878 1.46 145.1 CPP-15 C-3 1 0.040 0 4099 100 8 677 0.0449 5,973 11,373 16,861 1.48 142.4 CPP-16 C-3 1 0.040 0 4099 100 8 800 0.0541 6,088 13,248 19,370 1.46 143.5 CPP-17 C-4 1 0.025 0 4099 70 7.5 1801 0.0434 3,470 52,296 82,094 1.57 148.6 CPP-18 C-4 1 0.025 0 4099 70 7.5 1802 0.0488 3,900 61,091 90,275 1.48 148.6 CPP-19 C-4 1 0.025 0 4099 70 7.5 1800 0.0442 3,536 59,086 88,825 1.50 148.6 CPP-20 C-4 1 0.025 0 4099 100 7.5 1801 0.0390 3,118 15,807 22,904 1.45 140.2 CPP-21 C-4 1 0.025 0 4099 100 7.5 1800 0.0430 3,440 13,695 20,340 1.49 140.5 CPP-22 C-4 1 0.025 0 4099 100 7.5 1801 0.0257 2,055 12,323 18,027 1.46 138.7 CPP-23 C-5 1 0.050 0 4099 70 8 835 0.0617 5,321 50,959 76,581 1.50 149.5 CPP-24 C-5 1 0.050 0 4099 70 8 892 0.0612 4,941 52,441 79,829 1.52 149.9 CPP-25 C-5 1 0.050 0 4099 70 8 944 0.0650 4,959 56,232 84,346 1.50 150.0 CPP-26 C-5 1 0.050 0 4099 100 8 574 0.0544 6,821 13,376 20,509 1.53 141.6 CPP-27 C-5 1 0.050 0 4099 100 8 591 0.0525 6,400 12,253 19,016 1.55 141.2 CPP-28 C-5 1 0.050 0 4099 100 8 692 0.0520 5,408 11,035 17,207 1.56 140.3 CPP-29 C-6 1 0.080 0 4098 70 8 473 0.0755 7,180 38,184 55,893 1.46 148.5 CPP-30 C-6 1 0.080 0 4098 70 8 472 0.0712 6,788 42,195 62,468 1.48 148.9 CPP-31 C-6 1 0.080 0 4098 70 8 514 0.0701 6,136 44,454 65,482 1.47 148.9 CPP-32 C-6 1 0.080 0 4098 100 8 315 0.0689 9,830 10,219 15,820 1.55 139.9 CPP-33 C-6 1 0.080 0 4098 100 8 318 0.0680 9,629 10,457 16,104 1.54 140.3 CPP-34 C-6 1 0.080 0 4098 100 8 306 0.0686 10,088 10,129 15,608 1.54 139.9 CPP-35 C-7 1 0.025 3882 217 70 20 408 0.1750 61,765 62,517 97,293 1.56 140.5 CPP-36 C-7 1 0.025 3882 217 70 20 431 0.1740 58,175 69,889 108,627 1.55 141.2 CPP-37 C-7 1 0.025 3882 217 70 20 432 0.1907 63,640 61,091 97,955 1.60 140.8 CPP-38 C-7 1 0.025 3882 217 100 20 415 0.1515 52,632 18,730 29,690 1.59 125.4 CPP-39 C-7 1 0.025 3882 217 100 20 370 0.1541 59,909 18,572 29,223 1.57 126.1 CPP-40 C-7 1 0.025 3882 217 100 20 356 0.1456 58,944 17,362 27,869 1.61 124.0 CPP-41 C-8 1 0.025 3882 217 70 20 364 0.1904 75,406 60,930 94,347 1.55 141.5 CPP-42 C-8 1 0.025 3882 217 70 20 380 0.1988 75,256 57,535 91,377 1.59 140.8 CPP-43 C-8 1 0.025 3882 217 70 20 358 0.1979 79,647 57,913 86,184 1.49 140.8 CPP-44 C-8 1 0.025 3882 217 100 20 383 0.1593 59,925 17,058 25,017 1.47 123.7 CPP-45 C-8 1 0.025 3882 217 100 20 436 0.1557 51,459 17,111 23,752 1.39 123.8 CPP-46 C-8 1 0.025 3882 217 100 20 467 0.1560 48,092 17,179 24,443 1.42 124.6 CPP-47 C-8 2 0.025 3895 205 70 15 55 0.2504 653,217 21,157 38,868 1.84 134.2 CPP-48 C-8 2 0.025 3895 205 70 15 61 0.2475 580,456 19,457 38,646 1.99 134.1 CPP-49 C-8 2 0.025 3895 205 70 15 59 0.2017 495,645 21,606 39,801 1.84 134.2 CPP-50 C-8 2 0.025 3895 205 100 15 144 0.1442 144,200 8,239 13,042 1.58 107.4 CPP-51 C-8 2 0.025 3895 205 100 15 197 0.1303 95,487 8,824 13,934 1.58 109.9 CPP-52 C-8 2 0.025 3895 205 100 15 102 0.1615 228,224 7,313 11,542 1.58 105.8 CPP-53 C-9 1 0.060 0 4099 70 10 1209 0.0778 3860 22818 43504   1.91{circumflex over ( )} 150.9 CPP-54 C-9 1 0.060 0 4099 70 10 1409 0.0816 3475 27311 46621   1.71{circumflex over ( )} 150.9 CPP-55 C-9 1 0.060 0 4099 70 10 1374 0.0860 3755 24520 43853   1.79{circumflex over ( )} 150.9 CPP-56 C-9 1 0.060 0 4099 100 10 672 0.0693 6184 12335 100674   8.16{circumflex over ( )} 138.0 CPP-57 C-9 1 0.060 0 4099 100 10 723 0.0671 5570 5963 11233   1.88{circumflex over ( )} 138.5 CPP-58 C-9 1 0.060 0 4099 100 10 785 0.0676 5165 6905 11643   1.69{circumflex over ( )} 138.5 CPP-59 C-10 1 0.040 0 4099 70 8 1800 0.0261 1305 25078 43204   1.72{circumflex over ( )} 142.9 CPP-60 C-10 1 0.040 0 4099 70 8 1801 0.0299 1494 30110 46402   1.54{circumflex over ( )} 145.1 CPP-61 C-10 1 0.040 0 4099 70 8 1801 0.0339 1694 28609 49665   1.74{circumflex over ( )} 142.3 CPP-62 C-10 1 0.040 0 4099 100 8 1663 0.0498 2695 7424 13757   1.85{circumflex over ( )} 135.8 CPP-63 C-10 1 0.040 0 4099 100 8 1745 0.0486 2507 8065 13287   1.65{circumflex over ( )} 137.8 Total solvent volume: 4.1 ml {circumflex over ( )}GPC data from dual wavelength infrared detector used with Automation Studio software

TABLE 4 ¹³C NMR data for select polypropylene examples Cat Act Ex# ID ID T (C) m r mmmm mmmr rmmr mmrr PP-5 A 1 70 0.961 0.039 0.9013 0.0421 0.0031 0.0146 PP-10 A 1 100 0.970 0.030 0.9142 0.0333 0.0091 0.0170 PP-17 B 1 70 0.980 0.020 0.9316 0.0223 0.0136 0.0119 PP-22 B 1 100 0.961 0.039 0.8845 0.0504 0.0060 0.0247 PP-28 B 2 70 0.972 0.028 0.8972 0.0516 0.0115 0.0180 PP-33 B 2 100 0.955 0.045 0.8286 0.0935 0.0062 0.0463 PP-51 D 2 70 0.948 0.052 0.8631 0.0476 0.0144 0.0364 PP-57 D 2 100 0.860 0.140 0.6603 0.0985 0.0374 0.0699 PP-59-61 E 1 70 0.979 0.021 0.9526 0.0208 0.0017 0.0069 PP-62-64 E 1 100 0.934 0.066 0.8788 0.0258 0.0146 0.0176 PP-68-70 F 1 70 0.922 0.078 0.8213 0.0582 0.0161 0.0198 PP-74-76 F 1 100 0.837 0.163 0.5675 0.1698 0.0211 0.0732 PP-87 H 1 70 0.962 0.038 0.8926 0.0465 0.0060 0.0226 PP-92-94 H 1 100 0.806 0.194 0.5440 0.1468 0.0225 0.0069 PP-101-103 J 1 70 0.981 0.019 0.9552 0.0160 0.0011 0.0142 PP-104-106 J 1 100 0.934 0.066 0.8453 0.0527 0.0038 0.0401 PP-109 J 2 70 0.960 0.040 0.8603 0.0750 0.0055 0.0273 PP-114 J 2 100 0.851 0.149 0.5859 0.1820 0.0068 0.0785 PP-118 K 1 70 0.990 0.010 0.9753 0.0096 0.0012 0.0058 PP-120 K 1 100 0.971 0.029 0.9362 0.0161 0.0028 0.0208 PP-123-125 L 1 70 0.988 0.012 0.9275 0.0480 0.0059 0.0101 PP-132-135 L 1 100 0.970 0.030 0.8639 0.0765 0.0126 0.0261 PP-142 D 2 70 0.971 0.029 0.9265 0.0275 0.0026 0.0268 PP-145 D 2 100 0.934 0.066 0.8141 0.0699 0.0164 0.0541 PP-150 D 3 70 0.983 0.017 0.9533 0.0184 0.0021 0.0172 PP-151 D 3 100 0.958 0.042 0.8762 0.0499 0.0111 0.0333 CPP-5-7 C-2 1 70 0.755 0.245 0.5060 0.0788 0.0397 0.0714 CPP-8-10 C-2 1 100 0.777 0.223 0.5385 0.0905 0.0353 0.0633 CPP-11-13 C-3 1 70 0.955 0.045 0.8857 0.0406 0.0105 0.0023 CPP-23-25 C-5 1 70 0.930 0.070 0.8320 0.0312 0.0363 0.0153 CPP-26-28 C-5 1 100 0.923 0.077 0.7939 0.0632 0.0303 0.0216 CPP-29-31 C-6 1 70 0.968 0.032 0.8505 0.0871 0.0128 0.0236 CPP-32-34 C-6 1 100 0.947 0.053 0.7862 0.1146 0.0174 0.0399 CPP-53-55 C-9 1 70 0.936 0.064 0.8746 0.0357 0.0113 0.0205 CPP-56-58 C-9 1 100 0.911 0.089 0.8106 0.0557 0.0157 0.0419 2,1-regio stereo (ee) 1,3 regio defects/10000 defects/10000 defects/10000 ave. meso Ex# mmrm + rmrr rmrm rrrr mrrr mrrm monomer monomer monomer run length PP-5 0.0105 0.0029 0.0053 0.0029 0.0172 140.4 21.9 0.0 61.6 PP-10 0.0055 0.0034 0.0062 0.0006 0.0108 129.2 0.0 34.5 61.1 PP-17 0.0014 0.0126 0.0031 0.0002 0.0034 129.3 23.1 11.1 61.2 PP-22 0.0045 0.0105 0.0075 0.0045 0.0075 198.6 0.0 58.9 38.8 PP-28 0.0026 0.0026 0.0103 0.0000 0.0064 115.4 0.0 56.0 58.3 PP-33 0.0005 0.0062 0.0021 0.0005 0.0161 265.2 0.0 64.1 30.4 PP-51 0.0049 0.0039 0.0112 0.0020 0.0164 226.6 0.0 36.8 38.0 PP-57 0.0066 0.0517 0.0285 0.0022 0.0449 640.9 0.0 49.8 14.5 PP-59-61 0.0000 0.0002 0.0017 0.0001 0.0158 35.8 10.4 12.7 169.7 PP-62-64 0.0047 0.0070 0.0035 0.0012 0.0468 146.4 0.0 29.0 57.0 PP-68-70 0.0190 0.0136 0.0149 0.0097 0.0273 262.3 0.0 0.0 38.1 PP-74-76 0.0662 0.0168 0.0212 0.0021 0.0620 781.4 0.0 27.0 12.4 PP-87 0.0023 0.0090 0.0128 0.0023 0.0060 169.3 0.0 52.0 45.2 PP-92-94 0.0561 0.1226 0.0181 0.0484 0.0345 928.5 0.0 0.0 10.8 PP-101-103 0.0028 0.0014 0.0008 0.0013 0.0073 92.3 0.0 0.0 108.4 PP-104-106 0.0144 0.0094 0.0056 0.0038 0.0249 319.6 0.0 0.0 31.3 PP-109 0.0068 0.0041 0.0095 0.0000 0.0116 190.9 0.0 0.0 52.4 PP-114 0.0563 0.0171 0.0205 0.0051 0.0478 759.6 0.0 0.0 13.2 PP-118 0.0011 0.0015 0.0012 0.0016 0.0027 42.0 16.1 5.6 157.0 PP-120 0.0076 0.0038 0.0076 0.0005 0.0047 160.6 0.0 0.0 62.3 PP-123-125 0.0022 0.0012 0.0010 0.0005 0.0036 67.0 7.2 6.2 124.4 PP-132-135 0.0040 0.0043 0.0015 0.0009 0.0101 170.0 0.0 18.2 53.1 PP-142 0.0002 0.0021 0.0014 0.0005 0.0126 143.1 0 18.7 61.8 PP-145 0.0021 0.0109 0.0024 0.0009 0.0292 319.7 0 46.3 27.3 PP-150 0.0000 0.0015 0.0000 0.0000 0.0074 92.5 0 19.7 89.1 PP-151 0.0000 0.0092 0.0037 0.0018 0.0148 204.6 0 44.5 40.1 CPP-5-7 0.1244 0.0651 0.0260 0.0534 0.0352 1293.7 41.2 0.0 7.5 CPP-8-10 0.1082 0.0537 0.0280 0.0457 0.0369 1125.8 0.0 0.0 8.9 CPP-11-13 0.0192 0.0142 0.0067 0.0091 0.0118 176.4 15.8 15.2 48.2 CPP-23-25 0.0341 0.0125 0.0086 0.0155 0.0146 306.4 10.3 12.3 30.4 CPP-26-28 0.0289 0.0205 0.0092 0.0159 0.0164 352.7 0.0 14.4 27.2 CPP-29-31 0.0080 0.0038 0.0023 0.0015 0.0105 174.5 18.5 19.7 47.0 CPP-32-34 0.0071 0.0101 0.0041 0.0023 0.0183 277.7 0.0 41.3 31.3 CPP-53-55 0.0018 0.0057 0.0074 0.0005 0.0425 138.2 0.0 15.4 65.1 CPP-56-58 0.0046 0.0119 0.0080 0.0009 0.0506 284.0 0.0 26.7 32.2 **The following polymer samples were mixed for 13C NMR analysis: PP-59,60,61; PP-62,63,64; PP-68,69,70; PP-74,75,76; P-92,93,94; PP-101,102,103; PP-104,105,106; PP-123,124,125; P-132,133,134; CPP-5,6,7; CPP-8,9,10; CPP-11,12,13; CPP-23,24,25; CPP-26,27,28; CPP-29,30,31; CPP-32,33,34; CPP-53,54,55; CPP-56,57,58.

TABLE 5 Propylene polymerization examples and ethylene-propylene copolymerization examples quench Activity Cat Act Cat C2 Isohexane Toluene time yield (g P/mmol Mn Ex# ID ID (μmol) (psid) (uL) (uL) (s) (g) cat · hr) (g/mol) PP-154 B 2 0.020 0 3895 205 65 0.2586 715,023 46,062 PP-155 B 2 0.020 0 3895 205 83 0.2752 596,819 39,302 PP-156 B 2 0.020 0 3895 205 2700 0.0046 307 PP-157 B 2 0.020 0 3895 205 59 0.2770 849,404 34,546 EP-1 B 2 0.020 10 3875 205 26 0.3095 2,159,302 21,447 EP-2 B 2 0.020 10 3875 205 2703 0.0092 613 EP-3 B 2 0.020 10 3875 205 36 0.3245 1,645,352 22,171 EP-4 B 2 0.020 10 3875 205 35 0.3183 1,636,971 26,017 EP-5 B 2 0.020 20 3855 205 26 0.3405 2,375,581 16,265 EP-6 B 2 0.020 20 3855 205 80 0.2123 475,299 EP-7 B 2 0.020 20 3855 205 45 0.2801 1,115,442 36,877 EP-8 B 2 0.020 20 3855 205 38 0.3024 1,417,500 29,962 EP-9 B 2 0.020 40 3835 205 24 0.3484 2,646,076 14,649 EP-10 B 2 0.020 40 3835 205 23 0.3417 2,685,852 16,536 EP-11 B 2 0.020 40 3835 205 32 0.2937 1,672,975 25,256 EP-12 B 2 0.020 40 3835 205 25 0.3140 2,233,992 20,846 EP-13 B 2 0.020 60 3815 205 14 0.3670 4,652,113 10,774 EP-14 B 2 0.020 60 3815 205 17 0.3771 3,923,584 10,519 EP-15 B 2 0.020 60 3815 205 18 0.3575 3,535,714 13,639 EP-16 B 2 0.020 60 3815 205 22 0.3346 2,788,333 18,515 EP-17 B 2 0.020 80 3795 205 14 0.3527 4,439,580 9,386 EP-18 B 2 0.020 80 3795 205 17 0.3979 4,263,214 7,554 EP-19 B 2 0.020 80 3795 205 19 0.3275 3,054,404 15,229 EP-20 B 2 0.020 80 3795 205 2700 0.0105 700 127,605 PP-158 D 2 0.025 0 3869 231 38 0.3595 1,362,316 18,266 PP-159 D 2 0.025 0 3869 231 56 0.2441 632,201 33,752 PP-160 D 2 0.025 0 3869 231 44.8 0.2994 962,357 23,262 PP-161 D 2 0.025 0 3869 231 35.5 0.3364 1,364,552 14,140 EP-21 D 2 0.025 10 3849 231 2703 0 0 EP-22 D 2 0.025 10 3849 231 37 0.3332 1,303,826 19,688 EP-24 D 2 0.025 10 3849 231 22.6 0.3838 2,445,451 9,860 EP-25 D 2 0.025 20 3829 231 27 0.3580 1,916,431 16,025 EP-26 D 2 0.025 20 3829 231 24 0.3785 2,233,770 15,055 EP-27 D 2 0.025 20 3829 231 44.2 0.3127 1,018,751 26,928 EP-28 D 2 0.025 20 3829 231 22.2 0.3782 2,453,189 13,332 EP-29 D 2 0.025 40 3809 231 30 0.3248 1,585,464 22,187 EP-30 D 2 0.025 40 3809 231 16 0.3750 3,375,000 12,568 EP-31 D 2 0.025 40 3809 231 28.7 0.3441 1,726,495 22,990 EP-32 D 2 0.025 40 3809 231 17.5 0.3797 3,124,389 13,145 EP-33 D 2 0.025 60 3789 231 19 0.3609 2,794,065 13,721 EP-34 D 2 0.025 60 3789 231 15.6 0.4186 3,864,000 13,964 EP-35 D 2 0.025 60 3789 231 23.1 0.4037 2,516,571 17,450 EP-36 D 2 0.025 60 3789 231 15 0.4528 4,346,880 10,805 EP-37 D 2 0.025 80 3769 231 16 0.4306 3,827,556 10,100 EP-38 D 2 0.025 80 3769 231 10.6 0.4466 6,067,019 11,714 EP-39 D 2 0.025 80 3769 231 1409.3 0.0146 1,492 12,040 PP-162 E 1 0.040 0 0 4099 569.4 0.1013 16,012 116,598 PP-163 E 1 0.040 0 0 4099 510.6 0.1038 18,296 132,895 PP-164 E 1 0.040 0 0 4099 607.6 0.1028 15,227 131,661 PP-165 E 1 0.040 0 0 4099 608.1 0.0967 14,312 131,702 EP-40 E 1 0.040 10 0 4079 199.5 0.0979 44,165 136,095 EP-41 E 1 0.040 10 0 4079 254.8 0.1000 35,322 124,306 EP-42 E 1 0.040 10 0 4079 267.1 0.0970 32,684 123,579 EP-43 E 1 0.040 10 0 4079 320.8 0.0942 26,428 124,542 EP-44 E 1 0.040 20 0 4059 144.5 0.0990 61,661 127,569 EP-45 E 1 0.040 20 0 4059 185.8 0.1007 48,778 129,960 EP-46 E 1 0.040 20 0 4059 238.8 0.1094 41,231 125,210 EP-47 E 1 0.040 20 0 4059 233.5 0.0925 35,653 128,356 EP-48 E 1 0.040 40 0 4039 134.5 0.0917 61,361 141,798 EP-49 E 1 0.040 40 0 4039 121.5 0.1099 81,407 127,118 EP-50 E 1 0.040 40 0 4039 120.9 0.1072 79,801 128,520 EP-51 E 1 0.040 40 0 4039 145.1 0.0905 56,134 139,287 EP-52 E 1 0.040 60 0 4019 75.5 0.1154 137,563 148,160 EP-53 E 1 0.040 60 0 4019 92.9 0.1062 102,885 145,174 EP-54 E 1 0.040 60 0 4019 101.9 0.0933 82,404 158,085 EP-55 E 1 0.040 60 0 4019 107.8 0.1072 89,499 152,359 EP-56 E 1 0.040 80 0 3999 67 0.1089 146,284 160,566 EP-57 E 1 0.040 80 0 3999 62.7 0.1261 181,005 155,625 EP-58 E 1 0.040 80 0 3999 69.6 0.1145 148,060 159,207 EP-59 E 1 0.040 80 0 3999 82.6 0.1017 110,811 155,812 PP-166 J 2 0.080 0 3664 436 388.2 0.1230 14,258 7,175 PP-167 J 2 0.080 0 3664 436 395.3 0.1237 14,082 6,584 PP-168 J 2 0.080 0 3664 436 420.5 0.1230 13,163 6,510 PP-169 J 2 0.080 0 3664 436 397.6 0.1307 14,793 7,482 EP-60 J 2 0.040 10 3812 268 249.6 0.1068 38,510 11,683 EP-61 J 2 0.040 10 3812 268 263.1 0.1051 35,952 12,046 EP-62 J 2 0.040 10 3812 268 244.4 0.1153 42,459 12,490 EP-63 J 2 0.040 10 3812 268 253.6 0.1088 38,612 10,994 EP-64 J 2 0.040 20 3792 268 161.1 0.1091 60,950 13,665 EP-65 J 2 0.040 20 3792 268 225.8 0.1162 46,315 14,878 EP-66 J 2 0.040 20 3792 268 224.2 0.1149 46,124 12,859 EP-67 J 2 0.040 20 3792 268 190 0.1171 55,468 13,303 EP-68 J 2 0.040 40 3772 268 132.3 0.1275 86,735 18,949 EP-69 J 2 0.040 40 3772 268 119.5 0.1314 98,962 18,937 EP-70 J 2 0.040 40 3772 268 105.4 0.1276 108,956 21,114 EP-71 J 2 0.040 40 3772 268 100.5 0.1154 103,343 21,721 EP-72 J 2 0.040 60 3752 268 97.3 0.1311 121,264 20,069 EP-73 J 2 0.040 60 3752 268 82.6 0.1465 159,625 24,377 EP-74 J 2 0.040 60 3752 268 73.3 0.1423 174,720 24,661 EP-75 J 2 0.040 60 3752 268 69.8 0.1406 181,289 23,773 EP-76 J 2 0.040 80 3732 268 66.4 0.1605 217,545 28,148 EP-77 J 2 0.040 80 3732 268 73 0.1597 196,890 26,648 EP-78 J 2 0.040 80 3732 268 83.5 0.1375 148,204 34,280 EP-79 J 2 0.040 80 3732 268 81.2 0.1656 183,547 20,629 CPP-64 C-8 2 0.015 0 3843 257 85 0.2873 815,035 26,061 CPP-65 C-8 2 0.015 0 3843 257 88 0.2919 799,726 27,409 CEP-1 C-8 2 0.015 40 3803 257 30 0.2602 2,081,600 16,445 CEP-2 C-8 2 0.015 40 3803 257 34 0.2851 1,989,070 18,702 CEP-3 C-8 2 0.015 80 3763 257 22 0.2651 2,931,982 16,025 CEP-4 C-8 2 0.015 80 3763 257 24 0.2957 2,920,494 15,199 CPP-66 C-8 2 0.015 0 3843 257 85 0.3107 874,185 28,148 CPP-67 C-8 2 0.015 0 3843 257 98 0.3015 739,122 22,346 CEP-5 C-8 2 0.015 40 3803 257 35 0.2867 1,971,576 15,564 CEP-6 C-8 2 0.015 40 3803 257 38 0.2733 1,735,238 15,568 CEP-7 C-8 2 0.015 80 3763 257 22 0.3145 3,446,575 16,230 CEP-8 C-8 2 0.015 80 3763 257 24 0.3080 3,092,887 17,002 CPP-68 C-8 1 0.015 0 3925 175 811 0.1744 51,642 67,135 CPP-69 C-8 1 0.015 0 3925 175 925 0.1881 48,804 72,137 CEP-9 C-8 1 0.015 40 3885 175 88 0.1757 478,638 69,630 CEP-10 C-8 1 0.015 40 3885 175 87 0.1715 472,560 73,012 CEP-11 C-8 1 0.015 80 3845 175 52 0.2023 928,337 83,382 CEP-12 C-8 1 0.015 80 3845 175 59 0.2175 880,270 83,683 CPP-70 C-8 1 0.015 0 3925 175 876 0.1736 47,578 76,575 CPP-71 C-8 1 0.015 0 3925 175 974 0.1708 42,108 69,302 CEP-13 C-8 1 0.015 40 3885 175 91 0.1564 412,031 72,009 CEP-14 C-8 1 0.015 40 3885 175 79 0.1600 489,172 76,087 CEP-15 C-8 1 0.015 80 3845 175 48 0.1923 953,554 93,396 CEP-16 C-8 1 0.015 80 3845 175 55 0.2071 900,435 86,827 Mw C2 Tm % % % % Ex# (g/mol) PDI (wt %) (° C.) vinylene trisub vinyl vinylidene PP-154 82,621 1.79 0.0 150.6 PP-155 76,844 1.96 0.0 149.5 5.3 24.1 25.6 45.1 PP-156 PP-157 68,297 1.98 0.0 150.2 6.8 30.6 27.2 35.4 EP-1 55,205 2.57 5.8 119.8 EP-2 EP-3 61,185 2.76 6.1 127.5 2.8 6.9 18.6 71.7 EP-4 67,172 2.58 6.9 118.5 2.3 5.3 18.8 73.7 EP-5 50,898 3.13 8.2 125.3 0.6 4.8 20.8 73.8 EP-6 4.0 20.0 17.0 59.0 EP-7 75,986 2.06 7.2 108.4 EP-8 69,797 2.33 9.3 110.2 EP-9 45,724 3.12 12.4 113.2 EP-10 50,094 3.03 12.9 111.6 4.9 25.6 25.6 43.8 EP-11 61,842 2.45 14.0 98.7 7.9 34.2 25.0 32.9 EP-12 58,122 2.79 13.8 101.0 EP-13 43,719 4.06 16.4 109.4 1.4 7.7 23.9 67.1 EP-14 39,635 3.77 9.1 113.1 EP-15 48,900 3.59 11.7 105.1 1.1 4.9 22.7 71.4 EP-16 56,927 3.07 19.0 96.4 EP-17 17,399 1.85 22.1 95.2 EP-18 14,342 1.90 17.1 110.6 1.5 3.1 22.9 72.5 EP-19 52,278 3.43 22.6 2.3 5.1 19.8 72.9 EP-20 206,693 1.62 47.5 PP-158 63,815 3.49 0.0 147.6 PP-159 78,482 2.33 0.0 149.7 PP-160 66,799 2.87 0.0 148.1 4.9 16.7 54.2 24.3 PP-161 57,752 4.08 0.0 144.6 2.0 11.2 62.5 24.3 EP-21 EP-22 60,891 3.09 4.6* 113.9 3.3 9.0 54.9 32.8 EP-24 41,152 4.17 5.1* 105.2 0.5 5.4 64.5 29.6 EP-25 54,534 3.40 7.3 101.9 EP-26 57,503 3.82 7.2 103.9 1.2 3.5 63.5 31.8 EP-27 71,551 2.66 7.1 102.8 2.0 6.9 52.0 39.2 EP-28 53,053 3.98 4.3* 100.3 EP-29 64,761 2.92 9.1 85.9 EP-30 55,488 4.41 11.4 0.9 5.5 65.4 28.1 EP-31 69,600 3.03 11.0 EP-32 58,264 4.43 12.2 1.0 6.8 66.5 25.7 EP-33 56,519 4.12 11.1 EP-34 61,405 4.40 11.4 0.5 4.3 64.6 30.6 EP-35 65,640 3.76 9.6 EP-36 56,199 5.20 11.4 0.7 3.0 67.5 28.7 EP-37 51,849 5.13 17.7 0.4 5.6 65.6 28.4 EP-38 57,180 4.88 16.5 0.9 5.2 64.3 29.6 EP-39 34,026 2.83 11.5 PP-162 180,818 1.55 0.0 155.5 PP-163 208,482 1.57 0.0 155.3 9.4 15.6 46.9 28.1 PP-164 206,607 1.57 0.0 155.1 0.0 15.6 53.1 31.3 PP-165 208,146 1.58 0.0 155.2 EP-40 199,229 1.46 8.0 107.2 EP-41 192,436 1.55 7.8 106.9 1.5 1.5 16.7 80.3 EP-42 191,592 1.55 8.3 111.7 EP-43 191,762 1.54 8.3 109.0 0.0 5.8 14.5 79.7 EP-44 196,404 1.54 14.4 EP-45 200,749 1.54 12.7 3.4 5.1 16.9 74.6 EP-46 195,432 1.56 12.1 103.9 EP-47 201,150 1.57 18.1 1.6 11.1 14.3 73.0 EP-48 214,561 1.51 25.3 EP-49 199,200 1.57 23.9 EP-50 199,860 1.56 23.9 6.7 5.0 13.3 75.0 EP-51 215,039 1.54 27.2 0.0 2.0 12.0 86.0 EP-52 228,351 1.54 32.1 2.0 0.0 20.0 78.0 EP-53 226,315 1.56 29.2 EP-54 239,433 1.51 28.2 7.4 5.6 18.5 68.5 EP-55 237,910 1.56 37.1 EP-56 248,466 1.55 38.9 0.0 0.0 16.2 83.8 EP-57 245,882 1.58 42.7 EP-58 250,112 1.57 40.1 EP-59 245,004 1.57 34.4 0.0 0.0 15.4 84.6 PP-166 11,664 1.63 0.0 143.2 PP-167 10,527 1.60 0.0 142.1 0.6 1.5 19.7 78.2 PP-168 10,593 1.63 0.0 143.0 PP-169 12,126 1.62 0.0 143.7 1.3 1.6 19.5 77.6 EP-60 19,202 1.64 14.2 EP-61 19,644 1.63 14.1 EP-62 20,413 1.63 14.7 0.0 1.6 22.2 76.2 EP-63 17,886 1.63 14.4 0.9 2.3 22.1 74.8 EP-64 22,799 1.67 20.2 EP-65 24,324 1.63 19.0 0.0 0.0 22.8 77.2 EP-66 21,396 1.66 19.9 EP-67 22,489 1.69 18.7 0.0 0.0 22.4 77.6 EP-68 32,273 1.70 31.5 EP-69 32,981 1.74 28.8 0.0 0.0 23.8 76.2 EP-70 36,049 1.71 29.1 0.8 0.8 24.4 74.0 EP-71 35,704 1.64 32.2 EP-72 34,874 1.74 30.9 0.0 0.0 23.8 76.2 EP-73 43,447 1.78 31.9 0.0 1.0 24.8 74.3 EP-74 44,107 1.79 37.1 EP-75 42,399 1.78 39.5 EP-76 51,590 1.83 42.5 EP-77 49,844 1.87 42.2 0.0 0.0 24.2 75.8 EP-78 59,282 1.73 38.1 EP-79 38,534 1.87 33.9 0.0 0.0 22.9 77.1 CPP-64 43,859 1.68 0.0 134.3 CPP-65 46,039 1.68 0.0 134.9 4.3 1.1 9.8 84.8 CEP-1 33,304 2.03 23.6 CEP-2 34,664 1.85 23.1 0.0 9.7 17.0 73.3 CEP-3 47,570 2.97 36.8 CEP-4 44,512 2.93 33.6 1.7 2.2 17.2 78.9 CPP-66 45,267 1.61 0.0 134.5 CPP-67 41,469 1.86 0.0 134.2 0.0 9.0 13.0 78.0 CEP-5 32,020 2.06 19.5 CEP-6 32,767 2.10 19.2 2.9 19.5 18.0 59.5 CEP-7 47,215 2.91 37.3 CEP-8 47,432 2.79 35.7 2.4 7.3 20.0 70.2 CPP-68 103,027 1.53 0.0 141.4 CPP-69 107,978 1.50 0.0 142.0 0.0 11.8 19.7 68.4 CEP-9 105,159 1.51 46.5 148.2 CEP-10 109,924 1.51 47.3 150.3 2.9 10.1 14.5 72.5 CEP-11 132,653 1.59 54.2 126.8 CEP-12 131,961 1.58 54.6 6.3 35.9 25.0 32.8 CPP-70 113,564 1.48 0.0 142.1 CPP-71 103,118 1.49 0.0 142.0 3.3 37.4 22.0 37.4 CEP-13 107,954 1.50 46.6 136.3 CEP-14 112,919 1.48 46.9 1.6 6.3 12.7 79.4 CEP-15 139,551 1.49 54.8* CEP-16 133,620 1.54 53.4 103.1 6.1 18.4 20.4 55.1 Total solvent 4.1 ml, *outside calibration range.

All documents described herein are incorporated by reference herein, including any priority documents and/or testing procedures to the extent they are not inconsistent with this text. As is apparent from the foregoing general description and the specific embodiments, while forms of the invention have been illustrated and described, various modifications can be made without departing from the spirit and scope of the invention. Accordingly, it is not intended that the invention be limited thereby. Likewise, the term “comprising” is considered synonymous with the term “including.” Likewise whenever a composition, an element or a group of elements is preceded with the transitional phrase “comprising”, it is understood that we also contemplate the same composition or group of elements with transitional phrases “consisting essentially of,” “consisting of”, “selected from the group of consisting of,” or “is” preceding the recitation of the composition, element, or elements and vice versa. Likewise, the terms “comprising,” “consisting essentially of,” “consisting of” also include the product of the combinations of elements listed after the term. 

What is claimed is:
 1. A compound represented by the formula: T_(y)LAMX_(n-2) wherein: A is a substituted tetrahydro-as-indacenyl group bonded to M; L is substituted or unsubstituted monocyclic or polycyclic arenyl ligand or monocyclic or polycyclic heteroarenyl ligand bonded to M; M is a group 3, 4, 5, or 6 transition metal; T is a bridging group bonded to L and A; y is 0 or 1, indicating the absence or presence of T; X is a leaving group, typically a univalent anionic ligand, or two Xs are joined and bound to the metal atom to form a metallocycle ring, or two Xs are joined to form a chelating ligand, a diene ligand, or an alkylidene; n is the oxidation state of M and is 3, 4, 5, or 6, wherein the substituted tetrahydro-as-indacenyl group is derived from a tetrahydro-as-indacenyl ligand wherein the ligand is derived from tetrahydro-as-indacene isomers represented by the formula 4a or 4b:

wherein R³ is hydrogen or C₁-C₅₀ substituted or unsubstituted hydrocarbyl; each R¹, R², R⁴, and R⁵ is independently hydrogen, or a C₁-C₅₀ substituted or unsubstituted hydrocarbyl, halocarbyl or silylcarbyl; and each R^(a), R^(b), and R^(c) is independently C₁-C₅₀ substituted or unsubstituted hydrocarbyl, or hydrogen, wherein at least one R^(a), R^(b), and R^(c) is not hydrogen.
 2. The compound of claim 1, wherein M is a group 4 transition metal.
 3. The compound of claim 1, wherein M is zirconium or hafnium.
 4. The compound of claim 1, wherein each X is independently a halide, a hydride, an alkyl group, an alkenyl group or an arylalkyl group.
 5. The compound of claim 1 wherein the compound is represented by the formula 2:

wherein M is a group 3, 4, 5, or 6 transition metal; B is the oxidation state of M and is 3, 4, 5, or 6; C is B-2; T is a bridging group; y is 1 or 0 indicating the presence of absence of T; X is a leaving group; L is a substituted or unsubstituted monocyclic or polycyclic arenyl ligand or monocyclic or polycyclic heteroarenyl ligand bonded to M; each R¹, R², R⁴, and R⁵ is independently hydrogen, or a C₁-C₅₀ substituted or unsubstituted hydrocarbyl, halocarbyl or silylcarbyl; and each R^(a), R^(b), and R^(c) is independently C₁-C₁₀ alkyl, or hydrogen, wherein at least one R^(a), R^(b), and R^(c) is not hydrogen.
 6. The compound of claim 5, wherein B is
 4. 7. The compound of claim 5, wherein y is 1 and T is selected from (CR⁸R⁹)_(x), (SiR¹⁰R¹¹)_(x), CR⁸R⁹SiR¹⁰R¹¹, GeR¹⁰R¹¹, BR¹², NR¹², PR¹², O or S where x is 1 or 2, R⁸ and R⁹ are independently selected from hydrogen, substituted or unsubstituted hydrocarbyl, halocarbyl, silylcarbyl, R¹⁰, R¹¹ and R¹² are independently selected from substituted or unsubstituted hydrocarbyl, halocarbyl, or silylcarbyl and any two or more adjacent R⁸, R⁹, R¹⁰ or R¹¹ may optionally be bonded together to form a ring structure.
 8. The compound of claim 5, wherein each R^(a), R^(b), R^(c), R¹, R², R⁴ and R⁵ is independently hydrogen or a C₁-C₁₀ alkyl, wherein at least one R^(a), R^(b), and R^(c) is not hydrogen.
 9. The compound of claim 5, wherein R^(b) and R² are independently a C₁-C₁₀ alkyl.
 10. The compound of claim 5, wherein each R² is independently hydrogen, methyl, ethyl, propyl, butyl, pentyl or hexyl.
 11. The compound of claim 5, wherein R^(a) and R^(c) are independently hydrogen, methyl or ethyl.
 12. The compound of claim 5, wherein each R^(b) are independently hydrogen, methyl or ethyl.
 13. The compound of claim 5, wherein each R² is methyl or ethyl.
 14. A catalyst system comprising the compound of claim 1, and an activator.
 15. The catalyst system of claim 14, wherein the activator comprises a non-coordinating anion activator and/or an alumoxane.
 16. The catalyst system of claim 14, where the catalyst system is supported.
 17. A process to produce olefin polymer comprising contacting olefin monomer with the catalyst system of claim
 14. 18. The process of claim 17 wherein the monomer comprises ethylene and/or propylene.
 19. The process of claim 17, wherein the process occurs at a temperature of from about 0° C. to about 300° C., at a pressure in the range of from about 0.35 MPa to about 16 MPa, and at a time up to 300 minutes.
 20. The process of claim 17, wherein the olefin monomer comprises two or more of ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, or dodecene.
 21. The process of claim 17, wherein the olefin monomer comprises ethylene, propylene and 5-ethylidene-2-norbornene.
 22. A compound represented by the formula (3):

wherein M is a group 3, 4, 5, or 6 transition metal; B is the oxidation state of M and is 3, 4, 5, or 6; C is B-2; T is a bridging group; y is 1 or 0 indicating the presence of absence of T; X is a leaving group; each R¹, R², R⁴, and R⁵ is independently hydrogen, or a C₁-C₅₀ substituted or unsubstituted hydrocarbyl, halocarbyl or silylcarbyl; and each R^(a), R^(b), and R^(c) is independently C₁-C₁₀ alkyl, or hydrogen, wherein at least one R^(a), R^(b), and R^(c) is not hydrogen.
 23. The compound of claim 22, wherein M is zirconium or hafnium; B is 4; each X is independently a halide, a hydride, an alkyl group, an alkenyl group or an arylalkyl group; y is 1 and T is selected from (CR⁸R⁹)_(x), (SiR¹⁰R¹¹)_(x), CR⁸R⁹SiR¹⁰R¹¹, GeR¹⁰R¹¹, BR¹², NR¹², PR¹², O or S where x is 1 or 2, R⁸ and R⁹ are independently selected from hydrogen, substituted or unsubstituted hydrocarbyl, halocarbyl, or silylcarbyl, R¹⁰, R¹¹ and R¹² are independently selected from substituted or unsubstituted hydrocarbyl, halocarbyl, silylcarbyl and any two or more adjacent R⁸, R⁹, R¹⁰ or R¹¹ may optionally be bonded together to form a ring structure.
 24. The compound of claim 22, wherein each R^(a), R^(b), R^(c), R¹, R², R⁴ and R⁵ is independently hydrogen or a C₁-C₁₀ alkyl, wherein at least one R^(a), R^(b), and R^(c) is not hydrogen.
 25. The compound of claim 22, wherein each R² is independently hydrogen, methyl, ethyl, propyl, butyl, pentyl or hexyl.
 26. The compound of claim 22, wherein R^(a) and R^(c) are independently hydrogen, methyl or ethyl.
 27. The compound of claim 22, wherein each R^(b) is independently hydrogen, methyl or ethyl.
 28. The compound of claim 22, wherein each R² is methyl or ethyl.
 29. The compound of claim 22, wherein R^(b) and R² are independently a C₁-C₁₀ alkyl.
 30. The compound of claim 22, wherein y is 1 and T is selected from (CR⁸R⁹)_(x), (SiR¹⁰R¹¹)_(x), CR⁸R⁹SiR¹⁰R¹¹, GeR¹⁰R¹¹, BR¹², NR¹², PR¹², O or S where x is 1 or 2, R⁸ and R⁹ are independently selected from hydrogen, substituted or unsubstituted hydrocarbyl, halocarbyl, silylcarbyl, R¹⁰, R¹¹ and R¹² are independently selected from substituted or unsubstituted hydrocarbyl, halocarbyl, or silylcarbyl and any two or more adjacent R⁸, R⁹, R¹⁰ or R¹¹ may optionally be bonded together to form a ring structure.
 31. A catalyst system comprising the compound of claim 3, optional support, and an activator comprising a non-coordinating anion activator and/or an alumoxane.
 32. A process to produce olefin polymer comprising contacting olefin monomer with the catalyst system of claim
 31. 33. The process of claim
 32. wherein the olefin monomer comprises ethylene and/or propylene.
 34. The process of claim 32, wherein the olefin monomer comprises ethylene, propylene and 5-ethylidene-2-norbornene. 